JP2011162853A - Method for retreating tool for metalworking - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating a used tool for metalworking into a state of having enough oxidation resistance, while maintaining a superior performance of a titanium-based sintered body. <P>SOLUTION: The retreating method is a method for recycling the used tool for metalworking provided with a cermet substrate 11 formed of a sintered body in which titanium carbonitride is a main component of a hard phase. The method includes: a cleaning step of cleaning the cermet substrate 11; and a subsequent oxidation-resistant-film-forming step of forming an oxidation-resistant film 12 formed from a complex oxide containing titanium, on the surface of the cermet substrate 11. The cleaning step includes: an alkali cleaning treatment of cleaning the cermet substrate 11 with an alkaline aqueous solution; a water-washing treatment of washing the cermet substrate 11 with hot water after having completed the alkali cleaning treatment; and a dry treatment of blowing off the moisture on the surface of the cermet substrate with an air blow and air-drying the cermet substrate after having completed the water-washing treatment. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a metal processing tool reprocessing method for reusing a used metal processing tool, and a related technique.

  A titanium carbonitride-based sintered body (titanium carbonitride-based cermet) having titanium carbonitride (TiCN) as the main component of the hard phase and iron group metal as the main component of the binder phase has high hardness and strength, It possesses excellent characteristics such as being difficult to react with the alloy, good slipperiness with various metals, and low coefficient of friction, and metal such as metal pipe expansion dies, contraction dies, cutting tips, etc. It is suitably used as a processed product (metal processing tool).

  However, when TiCN-based cermets are exposed to an atmosphere in which oxygen is present at high temperatures, the constituent element titanium is oxidized and titanium oxide is generated on the cermet surface. Since this titanium oxide is brittle, when the metal is processed with a cermet tool on which the titanium oxide film is formed, the titanium oxide film falls off, the surface becomes rough, and the processing performance deteriorates. Furthermore, since the titanium oxide layer wears quickly, durability is also lowered.

  Therefore, conventionally, in order to improve the oxidation resistance of the titanium-based cermet, a method of adding another element to the component constituting the cermet has been proposed.

  For example, the cermet shown in Patent Document 1 is composed of a composite compound of chromium (Cr) and titanium (Ti) as a main component by containing chromium in a titanium-based sintered material, and improves oxidation resistance. I am doing so.

  On the other hand, many surface-coated cermet members in which a hard film is formed on a titanium-based sintered body have been proposed, although not intended to improve oxidation resistance.

  For example, the surface-covered cermet member disclosed in Patent Document 2 is such that a hard film containing titanium is formed on the surface of a cermet as a base material by CVD (chemical vapor deposition), PVD (physical vapor deposition), or the like.

  Furthermore, the surface-coated cermet member shown in Patent Document 3 has a hard film formed on the surface of the cermet base material, and in order to improve the adhesion of the hard film at the interface between the cermet base material surface and the hard film, An element containing layer is formed.

JP-A-2006-213977 (Claims) JP 2005-111623 (Claims) JP 2000-355777 (Claims)

  However, as shown in Patent Document 1, a cermet (sintered body) formed by adding another component to a component of a titanium-based sintered material has a component different from that of the titanium-based sintered body and is altered. Therefore, there is a problem that the excellent performance of the titanium-based sintered body is impaired.

  The surface-coated cermet member shown in Patent Document 2 simply forms a hard film by diffusion, but the diffusion amount differs between the binder phase (Co) of the cermet base material and the hard phase (TiC), for example, Since diffusion hardly progresses on the hard phase, the adhesion of the hard film is lowered, and there arises a problem that it is difficult to ensure sufficient oxidation resistance by peeling.

  The surface-covered cermet member shown in Patent Document 3 has a problem that the structure is complicated and difficult to manufacture because a diffusion element-containing layer is further formed at the interface between the hard film and the cermet base material. Will occur.

  The present invention has been made in view of the above-mentioned problems. By processing a used metal processing tool, the metal processing tool capable of improving the oxidation resistance while maintaining the excellent performance of the titanium-based sintered body. It is an object of the present invention to provide a method for reprocessing a metal working tool that can be easily manufactured, and a related technique.

  In order to achieve the above object, the present invention has the following structure.

[1] Recycle a used metal working tool provided with a cermet base material composed of a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride and titanium carbonitride A reprocessing method for use,
A cleaning step of cleaning the surface of the cermet substrate;
After the cleaning step is completed, a surface-coated cermet member that forms a metal processing tool after reprocessing is obtained by forming an oxidation resistant film composed of a composite oxide containing titanium on the surface of the cermet base material. Including an oxidation resistant film forming step,
The washing step includes
Alkaline washing treatment for washing the cermet base material with an alkaline aqueous solution;
A first water washing treatment for washing the cermet base material with hot water after the alkali washing treatment is completed;
After the first water washing treatment is completed, after the moisture on the surface of the cermet base material is blown off by air blow, the first drying treatment for natural drying is performed. .

  [2] The metal processing tool reprocessing method according to item 1, wherein in the cleaning step, the neutralization treatment with the acidic aqueous solution is performed after the alkali cleaning treatment and before the first water washing treatment.

  [3] In the cleaning step, after the first drying process is performed, a surface polishing process for polishing the surface of the cermet base material by a polishing tool is performed. Method.

  [4] The reprocessing method for a metal working tool as recited in the aforementioned Item 3, wherein in the cleaning step, after the surface polishing process is performed, the organic solvent cleaning process for cleaning the cermet base material is performed with an organic solvent.

  [5] The metal processing tool reprocessing method according to item 4, wherein in the cleaning step, after the organic solvent cleaning process is performed, a second water cleaning process is performed in which the cermet base material is cleaned with hot water.

  [6] The above-mentioned item 5, wherein, in the washing step, after the second water washing treatment is performed, the moisture of the cermet base material is blown off by air blow, and then the second drying treatment is naturally dried. Reprocessing method for metal working tools.

  [7] The metal processing tool reprocessing method according to any one of items 1 to 6, wherein the titanium compound is composed of titanium carbonitride.

  [8] The oxidation-resistant film is heated after applying a treatment liquid containing a metal salt that reacts with the titanium compound on the surface of the cermet base material to form the composite oxide on the cermet base material. 8. The reprocessing method for a metal working tool according to any one of items 1 to 7, which is formed by:

  [9] The metal processing tool reprocessing method according to [8], wherein an oxidation treatment is performed on the cermet base material in advance before the treatment liquid is applied.

  [10] The reprocessing method for a metal working tool according to any one of items 1 to 9, wherein the oxidation resistant film is formed of a perovskite complex oxide.

  [11] The metal processing tool reprocessing method according to [10], wherein the oxidation resistant film is formed by applying a treatment liquid containing an alkaline earth metal compound to the cermet base material and then heating the cermet base material.

  [12] The method for reprocessing a metal working tool according to any one of items 1 to 9, wherein the oxidation-resistant film is formed of an ilmenite-type composite oxide.

  [13] The metal-resisting tool according to item 12, wherein the oxidation-resistant film is formed by applying a treatment liquid containing a transition metal compound of an iron group divalent ion to the cermet base material and then heating it. Processing method.

  [14] The metal processing tool reprocessing method according to any one of [1] to [9], wherein the oxidation resistant film is formed of a spinel complex oxide.

  [15] The metal processing tool reprocessing method according to [14], wherein the oxidation resistant film is formed by applying a treatment liquid containing a magnesium compound or a cobalt compound to the cermet base material and then heating the cermet base material.

  [16] The method for reprocessing a metal working tool according to any one of items 1 to 15 above, wherein the thickness of the oxidation resistant film is 0.5 μm or less.

  [17] The method for reprocessing a metal working tool according to any one of items 1 to 16, wherein the complex oxide has a crystal structure in which oxygen ions are closely packed.

[18] An extrusion die for extruding an extruded material,
18. An extrusion die formed by a reprocessed metal working tool obtained by the reprocessing method according to any one of items 1 to 17.

[19] An extrusion method in which an extruded material is extruded by an extrusion die subjected to preheating,
As the extrusion die, while using the extrusion die according to the preceding item 18,
An extrusion processing method, wherein after the extrusion molding is started, the oxidation resistant film of the extrusion die is peeled off by a flowing extruded material.

[20] An oxidation resistant film is formed on the surface of a cermet base material composed of a sintered body containing at least one titanium compound of titanium carbide, titanium nitride and titanium carbonitride as a main component of the hard phase. A method of manufacturing a surface-coated cermet member,
A cleaning step of cleaning the surface of the cermet substrate;
After the cleaning step is completed, forming the oxidation-resistant film composed of a composite oxide containing titanium on the surface of the cermet, and obtaining the surface-coated cermet member,
The washing step includes
An alkali cleaning treatment for cleaning the surface of the used metal working tool with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the metal processing tool with hot water,
After the water washing treatment is completed, the moisture on the surface of the metal working tool is blown off by air blow, and then a drying treatment is performed to dry naturally.
The oxidation resistant film forming step includes:
A treatment liquid coating treatment for coating a treatment liquid containing a metal salt that reacts with the titanium compound on the surface of the cermet base material to form a composite oxide on the surface of the cermet base material,
A method for producing a surface-coated cermet member, wherein a heat treatment for forming an oxidation-resistant film is performed by heating after the coating.

[21] An oxidation resistant film is formed on the surface of a cermet base material composed of a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride, and titanium carbonitride. A method of manufacturing a surface-coated cermet member,
A cleaning step of cleaning the surface of the cermet substrate;
An oxidation resistant film forming step of obtaining the surface-coated cermet member by forming the oxidation resistant film composed of a composite oxide containing titanium on the surface of the cermet after the cleaning step is completed;
The washing step includes
Alkaline washing treatment for washing the cermet base material with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the cermet base material with hot water,
After the water washing treatment is completed, the moisture on the surface of the cermet base material is blown off by air blow, and then a drying treatment for natural drying is performed.
The oxidation resistant film forming step includes:
An oxidation treatment for oxidizing the cermet substrate by heating;
A treatment liquid coating treatment for coating a treatment liquid containing a metal salt that reacts with the titanium compound on the surface of the cermet base material to form a composite oxide on the surface of the cermet base material subjected to the oxidation treatment;
A method for producing a surface-coated cermet member, wherein a heat treatment for forming an oxidation-resistant film is performed by heating after the coating.

[22] A composite oxide containing titanium on the surface of a cermet base material composed of a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride and titanium carbonitride A method for forming an oxidation resistant film of a cermet base material that forms an oxidation resistant film constituted by:
Before forming the oxidation-resistant film on the cermet base material, including a cleaning step of cleaning the surface of the cermet base material in advance.
The washing step includes
Alkaline washing treatment for washing the cermet base material with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the cermet base material with hot water,
A method for forming an oxidation-resistant film on a cermet base material, wherein after the water washing treatment is completed, moisture on the surface of the cermet base material is blown off by air blow, followed by a drying process of natural drying.

[23] A method for preventing oxidation of a titanium-based sintered body for preventing oxidation in a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride, and titanium carbonitride. There,
A cleaning step of cleaning the surface of the sintered body;
After the cleaning step is completed, an oxidation resistant film forming step of forming an oxidation resistant film composed of a composite oxide containing titanium on the surface of the sintered body,
The washing step includes
Alkaline washing treatment for washing the sintered body with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the sintered body with hot water,
An anti-oxidation method for a titanium-based sintered body, characterized in that after the water washing treatment is completed, moisture on the surface of the sintered body is blown off by air blow, and then a drying treatment is performed for natural drying.

  According to the reprocessing method for a metal working tool of the invention [1], the reprocessed metal working tool contains at least one titanium compound selected from the group consisting of titanium carbide, titanium nitride, and titanium carbonitride in a hard phase. Since the surface of the titanium-based cermet base material composed of the sintered body as the main component is composed of a composite oxide containing titanium, while maintaining the excellent performance of the titanium-based sintered body, Can be improved. Further, after the cleaning process, it can be easily produced simply by forming an oxidation resistant film on the cermet substrate.

  According to the reprocessing method of the metal working tool of the invention [2] to [6], the cermet base material can be more reliably cleaned.

  According to the metal processing tool reprocessing method of the invention [7], a metal processing tool having excellent performance of the titanium carbonitride-based sintered body can be obtained.

  According to the metal processing tool reprocessing method of the invention [8], reprocessing can be performed more easily.

  According to the metal processing tool reprocessing method of the invention [9] to [15], a metal processing tool having even better oxidation resistance can be obtained.

  According to the metal processing tool reprocessing method of the invention [16], when the metal processing tool is reused, the smoothness after the oxidation resistant film is peeled off can be more reliably secured in the metal processing tool. it can.

According to the reprocessing method for a metal working tool of the invention [17], the oxidation resistant film has a crystal structure in which oxygen ions are closely packed, and thus has a stable structure in which oxygen ions are difficult to move. A metal working tool having an oxidation resistant film (passive film) excellent in oxidation resistance can be obtained.

According to the extrusion die of the invention [18], the same effect can be obtained as described above.

  According to the extrusion method of the invention [19], the same effect as described above can be obtained, and the excellent performance of the titanium-based sintered body can be obtained more reliably.

  According to the method for producing a surface-coated cermet member of the invention [20] or [21], the same effect can be obtained as described above.

  According to the oxidation resistant film forming method for a cermet base material of the invention [22], the same effect can be obtained as described above.

  According to the method for preventing oxidation of a titanium-based sintered body of the invention [23], the same effect can be obtained as described above.

FIG. 1 is a cross-sectional view schematically showing a surface-covered cermet member employed in an embodiment of the present invention. FIG. 2 is a block diagram showing an example of a manufacturing process of the surface-covered cermet member employed in the embodiment. FIG. 3 is a block diagram illustrating another example of the manufacturing process of the surface-covered cermet member employed in the embodiment. FIG. 4 is a sectional view schematically showing the periphery of an extrusion die of an extruder according to the first embodiment of the present invention. FIG. 5 is a graph showing the thermogravimetric change in the sample of the present invention and the comparative sample. FIG. 6 is a block diagram showing the process of the extrusion die reprocessing method according to the first embodiment of the present invention. FIG. 7 is a block diagram showing the process of the cleaning step in the reprocessing method of the first embodiment. FIG. 8 is a perspective view showing an extrusion die according to a second embodiment of the present invention. FIG. 9 is a perspective view showing the extrusion die of the second embodiment by cutting away. FIG. 10 is an exploded perspective view showing the extrusion die of the second embodiment. FIG. 11 is a side sectional view showing an extrusion die of the second embodiment. FIG. 12 is a perspective view showing a cutout of the main part of an extruder to which the extrusion die of the second embodiment is applied. FIG. 13 is a side sectional view showing the periphery of a die in the extruder according to the second embodiment. FIG. 14 is a perspective view showing a heat exchange tube manufactured by the extruder according to the second embodiment. FIG. 15 is a front sectional view showing a heat exchange tube according to the second embodiment.

<First Embodiment>
FIG. 1 is a cross-sectional view schematically showing a titanium-based surface-covered cermet member (1) used in an embodiment of the present invention. As shown in the figure, the surface-coated cermet member (1) includes a cermet base material (11) and an oxidation resistant film (12) provided on the cermet base material (11).

  The cermet base material (11) used for this embodiment is comprised by the sintered compact of the titanium carbonitride (TiCN). This TiCN-based sintered body (TiCN-based cermet) is composed of a hard phase mainly composed of titanium carbonitride (a component having a content of 50% by mass or more in the hard phase), nickel (Ni), cobalt (Co), etc. And a binder phase containing as a main component (a component whose content in the binder phase is 50% by mass or more).

  In the present invention, the main component of the hard phase in the cermet base material (11) is not limited to titanium carbonitride, and if it is at least one titanium compound of titanium carbide, titanium nitride, and titanium carbonitride, It can be employed as the main component of the hard phase. For example, a multi-component titanium compound such as TiCN-WC-TaC, TiC-WC-TaC can also be employed as the main component of the hard phase of the cermet base material (11). it can.

  Moreover, in this invention, a cermet base material is not necessarily limited to what is comprised only with a cermet. For example, a structure in which a cermet layer is provided on the surface of a material other than cermet such as die steel or ceramics may be used. Further, a method for providing a cermet layer on the surface of a material other than cermet such as die steel and ceramics is not particularly limited, but for example, a spraying method, a PVD method, or the like can be suitably used.

  The oxidation resistant film (12) is composed of a composite oxide containing titanium. The composite oxide containing titanium preferably has a crystal structure in which oxygen ions are closely packed. When the composite oxide has a crystal structure in which oxygen ions are closely packed, the oxide oxide film (passive film) has a stable structure in which oxygen ions are difficult to move and has excellent oxidation resistance. ) Can be formed.

Preferred examples of the composite oxide include perovskite (CaTiO ₃ ) type composite oxides, ilmenite (FeTiO ₃ ) type composite oxides, and spinel (MgAl ₂ O ₄ ) type composite oxides.

  Among them, the perovskite type complex oxide and the ilmenite type complex oxide have very high symmetry and stability in the crystal structure, can more reliably prevent the movement of oxygen ions, and are further excellent in oxidation resistance. An oxidation resistant film can be formed.

Examples of the perovskite complex oxide include oxides having a chemical composition such as CaTiO ₃ , SrTiO ₃ , and BaTiO ₃ .

This perovskite type complex oxide has a structure in which oxygen ions are close-packed in a face-centered cubic type, and cations having a large ion radius such as Ca ²⁺ , Sr ²⁺ , Ba ^2+, etc. It has a structure in which Ti ⁴⁺ ions having a small ion radius enter the gap between oxygen ions and cations, which are replaced with oxygen ions. In other words, it has a structure in which small Ti ⁴⁺ ions enter a gap between large divalent cations and oxygen ions packed in a close-packed state. This crystal structure is very stable, and as described above, oxygen ions are difficult to move.

The oxidation-resistant film (12) made of this perovskite complex oxide reacts an alkaline earth metal such as Ca, Sr or Ba with a titanium oxide such as titanium oxide (TiO ₂ ) produced on the surface of the cermet substrate. It is formed by making it.

The ilmenite-type complex _oxide, can be cited _{FeTiO 3, NiTiO 3, CoTiO 3} , MnTiO 3, MgTiO 3, oxide having a chemical composition such as a ZnTiO _3.

This ilmenite-type composite oxide has a crystal structure similar to corundum, and has a structure in which cations are inserted into the gaps between oxygen ions (6-coordinates) in a structure in which oxygen ions are packed in a hexagonal close-packed manner. ing. In other words, Fe ²⁺ , Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Mg ²⁺ , Zn ²⁺ ions, etc. with small ionic radii, and Ti ^{4 in} the gaps between the oxygen ions packed in the close-packed state. ^It has a structure with ⁺ ions. This crystal structure is also very stable and has a structure in which oxygen ions are difficult to move as described above.

  The oxidation resistant film (12) made of this ilmenite type complex oxide is composed of a transition metal of iron group divalent ions such as Fe, Ni, Co, Mn, Mg, Zn, and titanium oxide produced on the surface of the cermet substrate. It is formed by reacting.

Examples of the spinel complex oxide include oxides having chemical compositions such as MgTi ₂ O ₄ , Mg ₂ TiO ₄ , CoTi ₂ O ₄ , and Co ₂ TiO ₄ .

This spinel type complex oxide has a structure in which oxygen ions are close-packed in a face-centered cubic type. Spinel-type complex oxides containing Ti are crystals that are slightly inferior in stability due to differences in the charge of Ti ions. However, in practice, Ti ³⁺ ions are not observed, and even in the case of a composite oxide of the same element, Ti is a tetravalent Mg ₂ TiO ₄ spinel rather than a trivalent MgTi ₂ O _4. It is considered that it has a mold structure and has a structure in which Mg enters a so-called A site and Mg and Ti ⁴⁺ enter a B site.

  On the other hand, in the present invention, anatase type, rutile type, brookite type titanium oxide formed on the cermet base material (11) is not adopted as the oxidation resistant film (12). That is, these titanium oxides are not closely packed with oxygen ions and are not dense structures and are brittle. For example, in a high temperature aerobic environment of 450 ° C. or higher, the titanium oxide layer grows thick with time, In addition, innumerable cracks and holes are formed in the layer, and it is difficult to obtain sufficient oxidation resistance.

In addition, rutile-type titanium oxide has relatively high symmetry among titanium oxides, but has a crystal structure of TiO ₆ octahedron with a distorted center and lacks stability. Therefore, there are many gaps, oxygen ions easily move, and it is difficult to prevent oxidation.

  In the present invention, the thickness (T) of the oxidation resistant film (12) formed on the cermet base material (11) is adjusted to 0.5 μm or less, preferably 0.4 μm or less, more preferably 0.1 μm or more. Is good. That is, when this film thickness (T) is too thick, the surface from which the oxidation resistant film (12) is peeled off from the extrusion die constituted by the surface-coated cermet member (1) related to the present invention is rough as will be described later. There is a risk. Conversely, if the film thickness (T) is too thin, it may be difficult to obtain a sufficient antioxidant effect.

  Next, a process (an oxidation resistant film forming step) for forming the oxidation resistant film (12) on the cermet base material (11) will be described.

  As shown in FIG. 2, first, the cermet base material (11) is heated and oxidized, and then a treatment liquid containing a predetermined metal salt is applied to the surface of the cermet base material (11) (treatment liquid coating). processing). Thereafter, after drying, the cermet base material (11) is heated to cause the metal salt in the treatment liquid to react with titanium oxide (titanium oxide) on the surface of the cermet base material, thereby providing an oxidation resistant film (12). As a result, a composite oxide is produced.

  Here, the metal salt that reacts with titanium oxide to form a perovskite-type composite oxide is an alkaline earth metal such as Ca, Sr, or Ba, and this alkaline earth metal compound is contained in the treatment liquid. . Examples of the alkaline earth metal compound include calcium acetate (such as calcium acetate monohydrate).

  The metal salt that forms the ilmenite type complex oxide is a transition metal of an iron group divalent ion such as Fe, Ni, Co, Mn, Mg, Zn, and the transition metal compound is contained in the treatment liquid. Examples of the transition metal compound include nickel acetate (for example, Ni (II) acetate tetrahydrate).

  Moreover, the metal salt which produces | generates a spinel type complex oxide is a salt of Mg and Co, and these metal compounds are contained in the treatment liquid. Examples of the metal compound include cobalt acetate (for example, Co (II) acetate tetrahydrate).

  On the other hand, the treatment liquid containing a metal salt uses an aqueous or non-aqueous solvent depending on various additives to be added.

  Furthermore, the treatment liquid for film formation has a problem of “wetability” with the surface of the cermet base material (11). When this “wetting property” is poor, when the treatment liquid is applied to the surface of the cermet base material, it is repelled on the surface of the cermet base material, and a desired oxidation-resistant film (12) is formed due to insufficient application amount. May be difficult. Therefore, when the “wetting property” is poor, it is necessary to solve the problem. As this solution, the surface of the cermet base material (11) is oxidized with hydrogen peroxide water or heated in the atmosphere to oxidize, thereby forming an extremely thin oxide layer on the surface of the base material. The method can be suitably employed. Further, “wetting” can be improved by adding an appropriate additive such as a surfactant to the treatment liquid.

  Further, when applying the treatment liquid to the cermet base material (11), there is a problem of “sagging” of the treatment liquid depending on the viscosity of the treatment liquid. When this “sag” occurs, it becomes difficult to form a desired oxidation-resistant film (12) due to a shortage of processing liquid. In particular, since a three-dimensional shape always has a rising portion, “sag” is likely to occur at the rising portion. Therefore, in the case of a processing solution using an aqueous solvent, a water-soluble paste (thickening agent) is added to the processing solution in order to eliminate the “sag” problem, and an appropriate viscosity is given. Thus, it is preferable to perform subsequent steps such as a drying process and a heating process in a state in which the occurrence of “sag” is reliably prevented.

  Depending on the type and concentration of the paste, the coating film after moisture drying may peel off due to shrinkage or the like. The problem of shrinkage peeling can be solved by adding a water-soluble polyhydric alcohol having a relatively high boiling point as a plasticizer. By this addition, the film can maintain flexibility even after moisture drying.

  Further, when the solubility of the metal salt in the treatment liquid is small, precipitation of the metal salt may occur. This solubility problem can be solved by adding an organic acid such as formic acid, acetic acid, or citric acid to the treatment solution.

  When it is desired to keep the production temperature of the complex oxide low (for example, when it is desired to make it 500 ° C. or lower), a sodium salt (for example, sodium hydrogen carbonate) for producing the complex oxide at a low temperature is used as a reaction aid. What is necessary is just to add.

  As described above, the aqueous processing liquid includes a paste, a surfactant, a plasticizer, an organic acid, a reaction aid and the like in addition to the metal salt and the solvent, and is composed of a slurry or a paste having viscosity. Yes.

  Moreover, as a method of apply | coating a process liquid to the surface of a cermet base material (11), the process liquid is apply | coated with a brush etc., sprayed by spray etc., the method of immersing a cermet base material (11) in a process liquid, etc. Can be adopted.

  As described above, the treatment liquid is applied to the cermet substrate (11) and dried, and then the oxidation-resistant film (12) is generated by heating. The heating condition at the time of forming the film is sodium salt. In the case of non-addition, it is good to set in air at 380-700 ° C for 1-60 minutes, preferably at 570-620 ° C for 2-20 minutes. That is, if the heating temperature is too high, the progress of oxidation may surpass the formation of the oxidation resistant film (12). If the heating temperature is too low or the heating time is too short, the oxidation resistant film (12 ) May be insufficient, or the film thickness may be too thin to make it difficult to obtain a sufficient oxidation resistance effect.

  In the above example, oxidation treatment by heating is performed before the treatment liquid is applied to the cermet base material (11). As described above, it is preferable to promote the oxidation of titanium by heating before application of the treatment liquid, but this heat oxidation treatment is not always necessary and can be omitted. That is, as shown in FIG. 3, the treatment liquid is immediately applied to the cermet base material (11) without performing the heat oxidation treatment (treatment liquid application treatment), and then dried, and the oxidation resistant film formation treatment by heating. May be performed. Thus, even if oxidation treatment is not performed in advance, a titanium oxide film is generated on the surface of the cermet base material (11) to some extent during the formation of the oxidation resistant film, so that this titanium oxide reacts with the treatment liquid. As a result, a desired oxidation resistant film (12) is formed.

  As a matter of course, the oxidation treatment before applying the treatment liquid should be omitted in any case of forming any oxidation resistant film (12) of the perovskite complex compound, the ilmenite complex oxide and the spinel complex oxide. Can do.

  Thus, the oxidation resistant film (12) is formed on the surface of the titanium carbonitride-based cermet base material (11), and the TiCN-based surface-covered cermet member (1) related to the present invention is manufactured. In this surface-coated cermet member (1), the constituent components of the cermet base material (11) are the same as the constituent components of the TiCN-based sintered body, and the properties of the base material (11) do not change. The excellent performance possessed by the bonded body can be obtained with certainty.

  Furthermore, the surface-covered cermet member (1) related to the present invention can be easily produced simply by applying the treatment liquid to the cermet base material (11) and heating.

  In particular, since the titanium oxide film produced on the cermet base material (11) is reacted with the metal salt of the treatment liquid to form the oxidation resistant film (12), the types of elements contained in the cermet base material The oxidation resistant film (12) can be surely formed without being affected by the above, and the oxidation resistant film (12) can be formed more easily. As a result, the surface-coated cermet member (1) It can be made even easier.

  Further, as is apparent from the following experimental examples, the surface-coated cermet member (1) related to the present invention can improve oxidation resistance, particularly oxidation resistance under a high temperature environment.

  In the first embodiment, the surface-coated cermet member (1) is used as an extrusion die (metal working tool). Here, in the present invention, the entire extrusion die may be constituted by the surface-coated cermet member (1). However, in the present embodiment, only the die body (31) of the extrusion die (3) is surface-coated cermet. It is comprised with the member (1).

  Specifically, the extrusion die (3) of the extruder shown in FIG. 4 includes a die body (31) such as a bearing portion and a die holder (32) that supports the die body (31). The die body (31) of the extrusion die (3) is constituted by the surface-covered cermet member (1), and the die holder (32) is constituted by a steel material or the like. When the extrusion die (3) having this configuration is manufactured, for example, a cermet base material (11) as a die body (31) is shrink-fitted into a hot die holder (32), and then the cermet base material. As described above in (11), the oxidation resistant film (12) is formed, and the die body (31) is constituted by the surface-covered cermet member (1).

  The oxidation resistant film (12) may be formed on the entire peripheral surface of the die body (31), or may be formed only on the inner peripheral surface of the extrusion hole (bearing hole 33). In short, the oxidation resistant film (12) may be formed at least on a part of the inner peripheral surface of the extrusion hole (33).

  Moreover, in this invention, a die main body (31) says the member which forms the part of the internal peripheral surface of an extrusion hole.

  Here, if the temperature at which the oxidation-resistant film (12) is generated is a temperature exceeding the tempering temperature of the steel material, the hardness of the die holder (32) is lowered. It is necessary to carry out at a temperature below the tempering temperature of the steel material. In the case of SKD61 hot die steel, it is desirable to produce a complex oxide at 520 ° C. or lower. To meet this condition, for example, the temperature is adjusted to around 500 ° C. and the heating time is adjusted to about 30 minutes during film formation. Accordingly, an oxidation resistant film (12) having a film thickness of about 0.2 μm can be formed. The heating temperature at the time of film formation is lower than the general oxide film formation temperature, and the adhesion of the oxidation resistant film (12) to the cermet base material (11) is not so high. However, as will be described later, in this embodiment, the oxidation-resistant film (12) is required to be quickly removed (peeled) from the cermet base material (11) after the start of extrusion, and the oxidation-resistant film (12). Even if the adhesiveness is not so high, no problem occurs. Rather, it meets the requirement of quickly removing the oxidation resistant film (12) when necessary.

  Next, the case where extrusion molding is performed using the extrusion die (3) having the above configuration will be described. First, before actually performing extrusion molding, the extrusion die (3) is generally preheated in a preheating furnace. During this preheating, the extrusion die (3) is exposed to an oxygen atmosphere at a high temperature. However, since the die body (31) is constituted by the surface-coated cermet member (1), an oxidation resistant film ( 12) can prevent the cermet base material (11) from being oxidized and can prevent the formation of titanium oxide. Accordingly, embrittlement of the surface due to the generation of titanium oxide can be prevented, drop-off during extrusion molding performed later can be effectively prevented, and wear resistance and durability can be improved.

  When the preheating is completed, the extrusion mold (3) is set in the container (2) of the extruder, and extrusion molding is started. At the time of the extrusion molding, the extruded material (metal material F) in the container (2) flows toward the extrusion die (3) in a pressurized state, and the extruded material (F) is pushed into the extrusion hole (3) of the extrusion die (3). 33). On the other hand, when extrusion molding is started in this way, the oxidation-resistant film (12) of the surface-coated cermet member (1) constituting the die body (31) is scraped off by the extruded material (F) that flows under pressure. The oxidation resistant film (12) is removed (peeled) quickly. As a result, the die body (31) is constituted by a bare cermet substrate (11) without a film, and the die body (31) is held by the TiCN-based sintered body (cermet substrate) itself. Excellent performance (excellent performance such as hardly reacting with aluminum and its alloys) will be exhibited regretfully. For this reason, for example, the dimensional stability, strength, and hardness of the die body (31) can be sufficiently secured, the extrusion process can be performed smoothly in a stable state with high quality, and the surface state and the dimensional accuracy have high quality. An extruded product (extruded product) can be obtained, and early deterioration, breakage, and dropout can be prevented, and deterioration resistance, wear resistance, durability, and the like can be reliably improved. Moreover, weight reduction of a die | dye can also be implement | achieved by using a TiCN sintered compact as a die | dye.

  Here, in the first embodiment, when the extruded material is extruded 10 m from the start of extrusion, the oxidation resistant film (12) in the die main body (surface-coated cermet member 1) is 90% or more compared to before the start of extrusion. It is preferable to be configured to be peeled. That is, if the amount of peeling of the oxidation resistant film after extrusion is too small, it may be difficult to sufficiently exhibit the excellent performance possessed by the TiCN-based sintered body.

  The oxidation resistant film peeled from the die body (surface-coated cermet member) is included in the extruded material.

<Experimental example 1>
As in the first embodiment, a cermet base material composed of a titanium carbonitride-based sintered body is prepared, and Ni (II) acetate tetrahydrate 9 is used as a treatment liquid for forming an oxidation resistant film. .3 parts by mass, 4.7 parts by mass of polyvinylpyrrolidone (glue), 1.9 parts by mass of alkyl glucoside (surfactant), 5.6 parts by mass of glycerin (polyhydric alcohol), 4.9 parts by mass of citric acid, A mixture in which 6.5 parts by mass of sodium hydrogen carbonate (sodium salt) and 67.1 parts by mass of water were mixed was prepared.

After the treatment liquid is applied to the surface of the cermet base material, it is dried, and in the atmosphere (in the air), the temperature is raised to a temperature of 500 ° C. in a hot air circulating high-temperature furnace, and further maintained at 500 ° C. for 30 minutes, On the cermet base material, an oxidation resistant film composed of an ilmenite type complex oxide (NiTiO ₃ layer) was formed to obtain a surface-coated cermet member. In this case, the oxidation resistant film formed on the surface showed a blue interference color.

  The surface-coated cermet member thus obtained was tested for thermogravimetric change under the following conditions based on TGA (thermogravimetric analysis, thermogravimetric measurement).

  At this time, Shimadzu DTG60H was used as a test apparatus. Further, as a test sample of the surface-coated cermet member in this Experimental Example 1, a sample having a size of 3 mm × 4 mm × 0.15 mm was used, and this sample was accommodated in an alumina cell, and the above test apparatus was used. The thermogravimetric change was measured by setting the temperature rising rate to 1 ° C./min in the atmosphere (in the air). The measurement results are shown in FIG.

<Comparative Example 1>
A test similar to the above was performed using a cermet base material made of a titanium carbonitride-based sintered body similar to Experimental Example 1 in which an oxidation resistant film was not formed as a sample of a comparative example. The test results are also shown in FIG.

<Evaluation of oxidation resistance>
As is clear from FIG. 5, in the experiment example 1 having an oxidation resistant film, although the heating temperature is increased, the weight change (weight increase) is hardly observed and the oxidation is almost advanced. I understand that there is no.

  On the other hand, it can be seen that the comparative example without the oxidation resistant film increases in weight as the heating temperature rises and the oxidation proceeds. In particular, in the comparative example, the weight rapidly increases within the temperature environment range of the extrusion die, and it can be seen that oxidation proceeds rapidly in this temperature range.

  As described above, in the case of Experimental Example 1, even when exposed to an oxygen atmosphere at high temperatures, the cermet base material portion can be reliably prevented from being oxidized. Etc. can be effectively prevented.

<Experimental example 2>
As in the first embodiment, a cermet base material composed of a titanium carbonitride-based sintered body was prepared.

In addition, 9.8 parts by mass of calcium acetate monohydrate, 3.9 parts by mass of polyvinylpyrrolidone (glue), 1.4 parts by mass of alkyl glucoside (surfactant), 4.4 parts by mass of glycerin (polyhydric alcohol) Part, acetic acid 24.4 parts by mass, sodium acetate (sodium salt) 4.9 parts by mass, and a mixture of 51.2 parts by mass of water were prepared as a treatment liquid, and this treatment liquid was prepared on the surface of the cermet substrate. And heated to 500 ° C. in a hot air circulating high-temperature furnace (electric furnace) and held at 500 ° C. for 30 minutes, and a perovskite complex oxide (CaTiO ₃ layer on the cermet substrate) The surface-resistant cermet member of Experimental Example 2 was obtained. In this case, the oxidation resistant film had a slightly glossy silver gray color.

  When a test similar to the above was performed on the test sample comprising the surface-coated cermet member of Experimental Example 2, the same evaluation could be obtained. That is, also in Experimental Example 2, it was confirmed that there was no sudden increase in weight up to a temperature range of 600 ° C. and the oxidation resistance was excellent.

<Experimental example 3>
Co (II) acetate tetrahydrate 14.7 parts by mass, 6.2 parts by mass of polyvinylpyrrolidone (glue), 1.8 parts by mass of alkyl glucoside (surfactant), 2.1 of glycerin (polyhydric alcohol) A mixture obtained by mixing parts by mass and 75.2 parts by mass of water is prepared as a treatment liquid, and the treatment liquid is applied to the surface of a cermet base material made of the same titanium carbonitride-based sintered body as in Experimental Example 1, The temperature is raised in a hot air circulation type high temperature furnace (electric furnace) to a temperature of 600 ° C. in the air, and further maintained at 600 ° C. for 30 minutes to form a spinel complex oxide (Co ₂ TiO ₄ layer) on the cermet substrate. Thus, the surface-coated cermet member of Experimental Example 3 was obtained. In this case, although it was slightly dull, a glossy oxidation resistant film mainly composed of blue was observed.

  When a test similar to the above was performed on the test sample constituted by the surface-coated cermet member of Experimental Example 3, the same evaluation could be obtained. That is, also in Experimental Example 3, it was confirmed that there was no sudden weight increase up to a temperature range of 600 ° C. and the oxidation resistance was excellent.

  Next, in order to evaluate the oxidation resistance in actual use of the surface-coated cermet members of Experimental Examples 1 to 3 and Comparative Example 1 obtained as described above, the die of the extrusion die (3) shown in FIG. A main body (31) was constituted by each of the surface-coated cermet members (1), and an aluminum alloy round bar was extruded using the extrusion die (3).

  The extrusion die (3) was manufactured as follows. That is, after the cermet base material (11) constituting the die main body (31) is shrink-fitted into a die holder (32) made of a hot steel material, the above oxidation resistant film is formed on the cermet base material (11). Thus, the die body (31) was constituted by the surface-covered cermet member (1), and the extrusion mold (3) was manufactured. The heating temperature at the time of forming the oxidation resistant film was set to 500 ° C. and the heating time was set to 30 minutes, whereby an oxidation resistant film (12) having a thickness of 0.2 μm was formed.

  Next, when performing extrusion molding using the extrusion die (3), the extrusion die (3) was preheated at 450 ° C. for 300 minutes in a preheating furnace. Thereafter, the extrusion die (3) was set in the container (2) of the extruder, and an aluminum alloy round bar was extruded at a billet temperature of 450 ° C. The wear amount of the surface-covered cermet member (1) as the die body (31) when the extrusion length reached 50000 m was evaluated. Table 1 shows the evaluation results of the wear amount.

  As is apparent from Table 1, in the case of extrusion molding using an extrusion die using the surface-coated cermet members of Experimental Examples 1 to 3 of the present invention, the wear amount of the surface-coated cermet members is small, and there is sufficient durability as a die. Obtained.

  On the other hand, when extrusion molding was performed with an extrusion die using the cermet member of Comparative Example 1 in which an oxidation resistant film (surface coating) was not formed, the extrusion evaluation of 50000 m could not be performed, that is, the extrusion length. The wear amount of the cermet member reached 30 μm when the thickness reached 10000 m, and detachment due to oxidation was confirmed on the surface of the die after 10000 m extrusion. In Comparative Example 1, the wear was extremely fast compared to the system using the conventional WC-Co carbide material of Comparative Example 2.

<Reprocessing of Extrusion Die in First Embodiment>
In the first embodiment, the die body (31) of the extrusion die (3) made of the surface-coated cermet member used in the above-described extrusion process can be reused by reprocessing as described in detail below. A simple extrusion die (die body) is manufactured.

  The used die body (31) has most of its oxidation-resistant film (12) scraped off, and further on the surface is aluminum or an aluminum alloy material (metal material) as an extrusion molding material (molding material F). ) Is remaining and fixed.

  As shown in FIG. 6, the used extrusion die is subjected to a cleaning process (step S1) and then an oxidation resistant film forming process (step S2).

  In the cleaning process (step S1), as shown in step S11 of FIG. 7, the used die body is immersed in an alkaline aqueous solution, and the aluminum material as the extrusion molding material remaining and fixed to the extrusion die is immersed in the alkaline aqueous solution. And elute to remove (alkali washing treatment).

  As the alkaline aqueous solution used in the alkali cleaning treatment, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution having a temperature of 90 ° C. and a concentration of 12% is preferably used. Furthermore, an additive such as sodium gluconate may be mixed in the alkaline aqueous solution in order to increase the solubility of aluminum.

  In order to sufficiently remove the aluminum material, the immersion time is preferably set to at least 3 hours.

  After performing the alkali cleaning treatment, if necessary, neutralization treatment is performed using an acidic aqueous solution as shown in Step S12. As the acidic aqueous solution used for this neutralization treatment, an aqueous hydrochloric acid solution can be suitably used.

  After performing the neutralization process, as shown to step S13, a 1st water washing process is performed. In the first water washing treatment, the surface of the extrusion die is washed with hot water of about 80 ° C.

  After performing the 1st water washing process, as shown to step S14, a 1st drying process is performed. In the first drying process, first, water attached to the surface of the die is blown off by air blow and then naturally dried.

  Next, as shown in step S15, the surface state of the die body is visually observed or in some cases visually observed using an expansion scope to confirm whether the aluminum material on the die surface has been removed reliably (surface state confirmation). processing).

  Needless to say, when the surface condition is confirmed, if the removal of the aluminum material is insufficient, the process shown in steps S11 to S14 is repeated on the die body, or the surface of the die body is When the damage is severe, etc., the die body is discarded as non-recyclable.

  In addition, what is necessary is just to perform the process shown by the following steps S16-S19 including this surface state confirmation process (step S15) as needed, and does not necessarily need to be performed in this invention.

  After performing the surface state confirmation process, a surface polishing process is performed as shown in step S16. In this surface polishing treatment, for example, a # 1000 paper file is used to carefully polish the die surface.

  After performing the surface polishing process, as shown in step S17, an organic solvent cleaning process is performed. In this organic solvent cleaning treatment, the die surface is cleaned using an organic solvent such as ethanol or acetone.

  After performing the organic solvent cleaning process, as shown in step S18, the second water cleaning process is performed. In the second water washing treatment, the surface of the die is washed using hot water of about 50 ° C.

  After performing the 2nd water washing process, as shown to step S19, a 2nd drying process is performed. In the second drying process, similar to the first drying process, moisture attached to the surface of the die is blown off by air blow and then naturally dried.

  As a result, the cleaning process of the used extrusion die (die body) is completed, and the surface of the die is finished in the same good state as a new product.

  After the cleaning process is completed, an oxidation resistant film (12) is formed on the cleaned cermet substrate (11) as a die body as shown in step S2 of FIG. 6 by the oxidation resistant film forming process. To do.

  In this oxidation resistant film forming step, as shown in FIGS. 2, 3 and the like, a predetermined oxidation resistant film (12) is formed on the cermet substrate (11) in the same manner as described above, and the surface coated cermet member ( The die body (die body after reprocessing) constituted by 1) is manufactured.

  The method of using the extrusion die (die body) after this reprocessing is also used for extrusion in the same manner as described above.

  Also in the extrusion process using the reprocessed extrusion die, almost the same operational effects can be obtained as in the extrusion process using a new extrusion die as described above.

Second Embodiment
FIGS. 14 and 15 are views showing a heat exchange tube (160) as an extruded tube formed by an extrusion die (100) as a second embodiment of the present invention.

  As shown in both figures, the heat exchange tube (160) is made of aluminum or aluminum alloy used in a heat exchanger such as a condenser for a car air conditioner, and has a flat hollow shape. The hollow portion of the tube (160) is partitioned into a plurality of refrigerant flow paths (163) by a plurality of partition walls (162) extending in the tube length direction and arranged in parallel to each other. These refrigerant passages (163) extend in the tube length direction and are arranged in parallel along the tube width direction.

  As shown in FIGS. 8 to 11, the extrusion die (100) for manufacturing the heat exchange tube (160) includes a die case (120), a male die (130), a female die (140), The flow control plate (150) is provided as a basic component.

  The die case (120) has a hollow structure, and a dome portion (121) provided on the upstream side (rear side) with respect to the extrusion direction of the metal billet as the extruded material (extruded material), and the downstream side ( And a base portion (125) provided on the front side.

  In the dome portion (121), a surface (rear surface) facing the extrusion direction is formed as a pressure receiving surface (122). The pressure receiving surface (122) is formed in a hemispherical convex spherical surface protruding in the direction (rear direction) opposite to the extrusion direction.

  At the center of the peripheral wall of the dome portion (121), a male die holding hole (123) communicating with the hollow portion (weld chamber 112) inside is provided along the axis (A1). The male die holding hole (123) is formed in a flat rectangular shape corresponding to the cross-sectional shape of the male die (130).

  On both sides of the peripheral wall of the dome portion (121), a pair of port holes (124) (124) are formed on both sides of the axis. Each port hole (124) has a long hole shape extending in the circumferential direction, and is arranged to face each other at equal intervals in the circumferential direction. Further, the port hole (124) is arranged so as to approach the axis (A1) of the dome portion (121) as it goes downstream (front).

  In the present embodiment, the axial center of the die case (120) and the axial center of the dome portion (121) are configured to coincide with each other.

  The base portion (125) is formed integrally with the dome portion (121), and the outer peripheral surface is formed so as to protrude outward from the outer periphery on the other end side of the dome portion (121).

  A cylindrical female die holding hole (126) that communicates with the internal weld chamber (112) and corresponds to the cross-sectional shape of the female die (140) is formed inside the base portion (125). . The axis of the female die holding hole (126) is configured to coincide with the axis (A1) of the die case (120).

  Further, as shown in FIG. 10, key grooves (127) (127) parallel to the axis (A1) are formed on both side portions of the inner peripheral surface of the female die holding hole (126).

  The male die (130) is configured as a mandrel (131) in the main part of the first half. As shown in FIGS. 10 and 11, the front end of the mandrel (131) forms a hollow portion of the heat exchange tube (160), and a plurality of portions corresponding to each passage (163) of the heat exchange tube (160). It has a convex part (133) for channel formation. The plurality of passage-forming convex portions (133) are arranged at predetermined intervals in the width direction of the mandrel (131). Further, the gap provided between each of these passage-forming convex portions (133) is configured as a partition-forming groove (132) that forms a partition (162) of the heat exchange tube (160).

  The male die (130) is inserted into the male die holding hole (123) of the die case (120) from the pressure receiving surface (122) side and fixed. In this fixed state, the mandrel (131) of the male die (130) is arranged in a state protruding a predetermined amount from the male die holding hole (123) inside the die case (120).

  The base end surface (rear end surface) of the male die (130) is formed as a part of a spherical surface that follows the pressure receiving surface (122) of the die case (120), and the base end surface (rear side) of the male die (130). The end surface) and the pressure receiving surface (122) are configured to cooperate to form a desired smooth convex spherical surface.

  As shown in FIGS. 9 to 11, the female die (140) has a cylindrical shape, and key grooves of the female die holding hole (126) in the die case (120) are formed on both sides of the outer peripheral surface. Corresponding to (127) and (127), key protrusions (147) and (147) parallel to the axis are formed.

  The female die (140) has a die hole (bearing hole 141) that is open to the rear end surface side and formed corresponding to the mandrel (131) of the male die (130), and a die hole (141). A relief hole (142) that is open to the front end face side is provided.

  The die hole (141) is provided with an inward projecting portion along the inner peripheral edge thereof so that the outer peripheral portion of the heat exchange tube (160) can be formed. Furthermore, the relief hole (142) is formed in a taper shape that widens toward the front end side (downstream side) so that the thickness (height) gradually increases, and is opened downstream.

  The flow control plate (150) has a circular outer shape corresponding to the cross-sectional shape of the female die holding hole (126) in the die case (120). Further, a central through hole (151) is formed in the center of the flow control plate (150) corresponding to the mandrel (131) of the male die (130) and the die hole (141) of the female die (140). ing.

  As shown in FIG. 10, the both sides of the outer peripheral edge of the flow control plate (150) correspond to the key grooves (127) (127) of the female die holding hole (126) in the die case (120). Thus, key protrusions (157) and (157) are formed.

The female die (140) is housed and fixed in the female die holding hole (126) of the die case (120) via the flow control plate (150). At this time, the key protrusions (147) and (147) of the female die (140) and the key protrusions (157) and (157) of the flow control plate (150) are key grooves (127) and (127) of the female die holding hole (126). ) Is positioned in the direction around the axis. And male die (1
The mandrel (131) of 30) and the die hole (141) of the female die (140) are disposed corresponding to the central through hole (151) of the flow control plate (150). As a result, the mandrel (131) of the male die (130) is disposed inside the die hole (141) of the female die (140), and a flat annular extrusion is formed between the mandrel (131) and the die hole (141). A hole (111) is formed. Further, the extrusion hole (111) has a shape corresponding to the cross-sectional shape of the heat exchange tube (60), in which a plurality of partition forming grooves (132) of the mandrel (131) are arranged in parallel in the width direction. ing.

  In the second embodiment, among the constituent members of the extrusion die (100), the female die (140) is constituted by the surface-covered cermet member (1) used in the first embodiment. is there.

  Here, in the second embodiment, an oxidation resistant film (12) may be formed on the entire peripheral surface of the female die (140) as the cermet base material (11), or the female die (140) The oxidation resistant film (12) may be formed only on the inner peripheral surface of the die hole (141).

  In the second embodiment, the die body is constituted by the female die (130).

  In the present invention, among the constituent members of the extrusion die (100), the constituent members other than the female die (140), such as the male die (130), are constituted by the surface-coated cermet member (1). You may make it do.

  Furthermore, in the present invention, the inner peripheral surface of the extrusion hole includes not only the inner peripheral surface of the die hole in the female die, but also the outer peripheral surface of the mandrel in the male die.

  The extrusion die (100) of the second embodiment configured as described above is set in an extrusion molding machine as shown in FIGS. That is, the extrusion die (100) is set in the container (6) in a state of being attached to the die installation hole (5a) provided in the center of the plate (5). The extrusion die (100) is fixed in the direction orthogonal to the extrusion direction by the plate (5) and fixed in the extrusion direction by a backer (not shown). The extrusion die (100) is generally preheated before extrusion (before being set in a container), as in the first embodiment. At the time of this preheating, the extrusion die (100) is fixed by a plate (5) and a backer (not shown), and at the time of die preheating, the set of these dies are preheated together.

  Then, a metal billet (extrusion material) such as an aluminum billet inserted into the container (6) is pushed through the dummy block (7) in the right direction (extrusion direction) in FIG. Thereby, the metal billet is pressed against the pressure receiving surface (122) of the die case (120) in the extrusion die (100) and plastically deforms. Thus, while the extruded material is plastically deformed, the extruded material is introduced into the weld chamber (112) of the die case (120) through the pair of port holes (124) (124), and is further pushed forward through the extrusion hole (111). As a result, the extruded material is formed into a cross-sectional shape corresponding to the opening shape of the extrusion hole (111), and the heat exchange tube (160) having the above shape is manufactured.

  On the other hand, when extrusion molding is started in this way, the oxidation-resistant film (12) of the surface-coated cermet member (1) constituting the female die (140) is scraped off by the extruded material (metal billet) that flows under pressure. Thus, the oxidation resistant film (12) is quickly removed (peeled). Thereby, the die hole inner peripheral surface (bearing hole inner peripheral surface) of the female die (140) is constituted by the exposed cermet base material (11) without a film, and the female die (140) is formed. The excellent performance of the TiCN-based sintered body (cermet base material) itself (excellent performance such as being difficult to react with aluminum and its alloys) can be exhibited without regret. For this reason, for example, the dimensional stability, strength, and hardness of the female die (140) can be sufficiently secured, the extrusion process can be performed smoothly in a stable state with high accuracy, and the surface state and dimensional accuracy are high. The heat exchange tube can be obtained, and early deterioration, breakage, and dropout can be prevented, and the deterioration resistance, wear resistance, durability, and the like can be reliably improved. Moreover, weight reduction of a die | dye can also be implement | achieved by using a TiCN sintered compact as a die | dye.

  <Experimental example 11>

As shown in Table 2, an extrusion die (100) similar to that of the second embodiment was prepared. At this time, as a female die (140) of the extrusion die (100), a titanium carbonitride-based cermet is used as the base material of the die (140), and the ilmenite type composite is formed on the surface of the base material in the same manner as in Experimental Example 1. It was prepared which was formed a surface coating layer (oxidation film) composed of an oxide (NiTiO ₃ layers).

  Of the constituent members of the extrusion die (100), those other than the female die (140) are made of steel.

  Further, the extrusion die (100) was preheated at 420 ° C. for 8 hours, and extrusion was performed in the same manner as in the second embodiment.

  And the extrusion length (extrusion amount per die | dye) until the outer surface roughness of the heat exchange tube (160) as an extrusion product (extruded product) exceeds 5 micrometers was measured.

<Experimental example 12>
As shown in Table 2, extrusion was performed in the same manner as in Experimental Example 11 except that the preheating temperature of the extrusion die (100) was 450 ° C. and the preheating time was 4 hours, and the same measurement was performed. It was.

<Experimental example 13>
As shown in Table 2, extrusion was carried out in the same manner as in Experimental Example 12 except that the preheating time was 8 hours, and the same measurement was performed.

<Experimental Example 14>
As shown in Table 2, extrusion was performed in the same manner as in Experimental Example 12 except that the preheating time was 24 hours, and the same measurement was performed.

<Experimental Example 15>
As shown in Table 2, extrusion was performed in the same manner as in Experimental Example 12 except that the preheating time was 28 hours, and the same measurement was performed.

<Experimental Example 16>
As shown in Table 2, extrusion was carried out in the same manner as in Experimental Example 12 except that the preheating temperature was 500 ° C. and the preheating time was 24 hours, and the same measurement was performed.

<Experimental Example 17>
As shown in Table 2, extrusion was performed in the same manner as in Experimental Example 12 except that the preheating temperature was 520 ° C. and the preheating time was 24 hours, and the same measurement was performed.

<Comparative Example 11>
As shown in Table 2, as a female die (140) of the extrusion die (100), a surface coating layer composed of a titanium carbonitride cermet as a base material and an anatase type oxide on the inner peripheral surface of the die hole What formed was used. As described in detail in the first embodiment, the anatase type titanium oxide is different from the oxidation resistant film of the present invention.

  Using this extrusion die (100), extrusion was performed in the same manner as in Experimental Example 12, and the same measurement was performed.

<Comparative Example 12>
As shown in Table 2, using a female die (140) having no oxide film on the inner peripheral surface of the die hole, extruding was performed in the same manner as in Comparative Example 11 except that the preheating temperature was 420 ° C. Similar measurements were made.

<Comparative Example 13>
As shown in Table 2, extrusion was carried out in the same manner as in Comparative Example 11 except that the preheating temperature was 420 ° C. and the preheating time was 6 hours, and the same measurement was performed.

<Comparative example 14>
As shown in Table 2, extrusion was performed in the same manner as in Experimental Example 12 except that a female die (140) made of WC-Co cemented carbide was used and the preheating time was 6 hours. The same measurement was performed.

<Evaluation>
As shown in Comparative Examples 11 and 13, in an extrusion die (100) in which a titanium carbonitride cermet base material on which an oxidation resistant film is not formed is a female die (140), the preheating temperature is set to 450 ° C. ( In the comparative example 1) or the preheating time set to 6 hours (comparative example 3), the extrusion length is very short. Furthermore, the inner peripheral surface (bearing surface) of the die hole is also violently rough, and has a major problem with the durability life due to early wear. Moreover, as shown in Comparative Example 2, when the preheating was performed at 420 ° C. for 4 hours, the extrusion length was relatively long, and good results were obtained. Judging from these results, when the titanium carbonitride cermet base material on which the oxidation resistant film is not formed is a female die (140) (Comparative Examples 11 to 13), the preheating temperature is 420 ° C. and the preheating time is. It seems that 4 hours is the upper limit, and if preheating exceeding this is performed, it is considered that a problem due to the generation of titanium oxide occurs.

  In addition, although the thing of the comparative example 12 is a thing whose extrusion length is comparatively long, in such preheating conditions, since the heating conditions (temperature x time) are low for the die (die) used for extrusion processing, The extrusion pressure becomes high, and it becomes difficult to perform the extrusion process smoothly. Furthermore, since preheating conditions are very limited, it is difficult to control the temperature, and it seems impossible to adopt it for actual production.

  Moreover, compared with the comparative examples 11 and 13, the thing of the comparative example 14 can obtain a reasonable evaluation even if the heating temperature at the time of preheating is increased, and the restrictions on the preheating conditions are slightly relaxed. .

  On the other hand, as shown in Experimental Examples 11 to 14, in the case where the titanium carbonitride cermet base material on which the oxidation resistant film is formed is a female die (140), the heating temperature at the time of preheating is slightly increased. However, the extrusion length could be made sufficiently long regardless of the heating time.

  Further, as shown in Experimental Examples 15 to 17, even if the preheating temperature was set to a very high temperature or the heating time was set to be very long, the extrusion length could be secured to a certain extent. Therefore, the experimental examples 11 to 17 related to the present invention can greatly reduce the restrictions on the preheating conditions, can easily perform the temperature control, and can be suitably used for actual production. In Examples 11 to 14, it is considered that the extrusion length can be further ensured, the durability life is long, and efficient productivity can be ensured.

Specifically, in the case of using a female die in which an oxidation resistant film of an ilmenite type composite oxide (NiTiO ₃ layer) is formed on the surface of a titanium carbonitride cermet base material, that is, a female type related to the present invention. In the case of using a die, the heating temperature can be set to 420 to 520 ° C., more preferably 450 to 500 ° C. as the preheating condition, and the heating time is 28 hours or less, preferably 4 hours or more, more preferably 24 hours or less. Can be set to

The above experimental examples 11 to 17, the surface of the titanium carbonitride-based cermet substrate, but those using a female die forming the oxidation film of ilmenite-type complex oxide (NiTiO ₃ layers), the As in Experimental Example 2, using a female die in which an oxidation-resistant film of perovskite complex oxide (CaTiO ₃ layer) is formed on the surface of a titanium carbonitride cermet base material, or as in Experimental Example 3 above In addition, a female die in which an oxidation resistant film of a spinel composite oxide (Co ₂ TiO ₄ layer) is formed on the surface of a titanium carbonitride-based cermet base material is used, as in Experimental Examples 11 to 17 above. When the same measurement was carried out by performing extrusion processing, the same evaluation as in the above Experimental Examples 11 to 17 could be obtained. Therefore, the oxidation resistant film is not limited to the ilmenite type complex oxide (NiTiO ₃ layer) as shown in the above experimental examples 11 to 17, but the perovskite type complex oxide (CaTiO ₃ layer) or the spinel type complex oxide (Co ₂ TiO ₄ layer), the same conditions as described above can be set as preheating conditions.

<Reprocessing of Extrusion Die in Second Embodiment>
Also in the female die (140) of the extrusion die (100) used for the extrusion process in the second embodiment, the reusable female die (140) can be obtained by reprocessing as in the first embodiment. ) Can be produced.

  That is, the used female die (140) is cleaned in the same manner as in step S1 of FIG. In this cleaning step, as described above, as shown in FIG. 7, an alkali cleaning process (step S11), a neutralization process (step S12), a first water washing process (step S13), and a first drying process (step S14). The surface condition confirmation process (step S15), the surface polishing process (step S16), the organic solvent cleaning process (step S17), the second water washing process (step S18), and the second drying process (step S19) are sequentially performed as necessary. Do.

  The cermet base material (11) as the used female die (140) washed in this manner is subjected to the oxidation resistant film (12) in the same manner as described above, as shown in step S2 of FIG. 6 and FIGS. Form. Thus, a female die (140) constituted by the surface-coated cermet member (1) having the oxidation resistant film (12) formed on the cermet base material (11) is manufactured.

  When the extrusion die (100) provided with the reprocessed female die (140) is extruded in the same manner as described above, the extrusion die (100) provided with the new female die (140) is obtained. Similar to the extrusion process used, almost the same effect can be obtained.

  In each of the above embodiments, the case where the metal processing tool to be reprocessed is configured by an extrusion die (die body, female die) or the like has been described as an example. However, the present invention is not limited thereto, and in the present invention. The reworked metal working tools include drawing dies such as expansion dies and contraction dies, warm and cold forging dies, die casting dies, bending dies, The present invention can also be applied to cutting machine tools such as cutting tips and cutting tools, as well as metal working dies (dies) such as rolls for cold and cold rolling and casting molds.

  <Reference Example 1>

As shown in Table 3, an extrusion die (100) similar to that of Experimental Example 11 was prepared. That is, as a female die (140), a carbonitriding cermet is used as the base material of the die (140), and a surface coating layer (oxidation resistant) composed of an ilmenite composite oxide (NiTiO ₃ layer) is formed on the surface of the base material. What formed the film | membrane) was prepared.

  This extrusion die (100) was preheated at 450 ° C. for 8 hours, and then extruded in the same manner as in Experimental Example 11.

  And when the extrusion length reaches 30000 m, the surface roughness of the heat exchange tube (160) as an extruded product is measured, and when the surface roughness is 5 μm or less, the surface condition is “good (good)”. ".

<Example 1>
As shown in Table 3, with respect to the used female die (140) used in Reference Example 1, as in the second embodiment, a cleaning process (step S1 in FIG. 6) and an oxidation resistant film forming process ( Step S2) of the figure was performed, and the female die (140) was reprocessed into a reusable state. At this time, the oxidation resistant film was made of an ilmenite type complex oxide (NiTiO ₃ layer) as in Reference Example 1.

  Then, using the female die (140) after the reprocessing, extrusion was performed in the same manner as in Reference Example 1, and the same evaluation was performed.

<Reference Example 2>
As shown in Table 3, a female die (140) having an oxidation resistant film composed of a perovskite compound (CaTiO ₃ layer) was prepared. This oxidation resistant film was formed in the same manner as in Experimental Example 2.

  Using the extrusion die (100) provided with the female die (140), extrusion was performed in the same manner as in Reference Example 1, and the same evaluation was performed.

<Example 2>
As shown in Table 3, the used female die (140) used in Reference Example 2 was washed in the same manner as in Example 1 and then an oxidation resistant film was formed in the same manner, thereby forming the female die. (140) was finished in a reusable state. At this time, the oxidation resistant film was made of a perovskite type compound (CaTiO ₃ layer) as in Reference Example 2.

  Then, using the female die (140) after the reprocessing, extrusion was performed in the same manner as in Reference Example 2, and the same evaluation was performed.

<Reference Example 3>
As shown in Table 3, a female die (140) having an oxidation resistant film composed of a spinel complex oxide (Co ₂ TiO ₄ layer) was prepared. This oxidation resistant film was formed in the same manner as in Experimental Example 3 above.

  Using the extrusion die (100) provided with the female die (140), extrusion was performed in the same manner as in Reference Example 1, and the same evaluation was performed.

<Example 3>
As shown in Table 3, the used female die (140) used in Reference Example 3 was washed in the same manner as in Example 1, and then an oxidation-resistant film was formed in the same manner, thereby forming the female die ( 140) was finished in a reusable state. At this time, the oxidation resistant film was formed of a spinel complex oxide (Co ₂ TiO ₄ layer) as in Reference Example 3.

  Then, using the female die (140) after the reprocessing, extrusion was performed in the same manner as in Reference Example 2, and the same evaluation was performed.

<Summary>
As is apparent from the comparison between Example 1 and Reference Example 1, the comparison between Example 2 and Reference Example 2, and the comparison between Example 3 and Reference Example 3, the used female die (140) is formed according to the present invention. The female die (140) could be regenerated like a new product by reprocessing by means related to. Further, according to the reprocessing by the means related to the present invention, the oxidation resistant film comprises an ilmenite type complex oxide (NiTiO ₃ layer), a perovskite type compound (CaTiO ₃ layer) and a spinel type complex oxide (Co ₂ TiO ₄ layer). ) Were able to be reproduced as if they were new.

  The metal processing tool reprocessing method of the present invention can be applied to a metal processing technique for processing a metal material with a metal processing tool.

1: Surface-covered cermet member 11: Cermet base material 12: Oxidation resistant film 31: Die body (metal working tool)
140: Female die (metal working tool)
F ... Extruded material (metal material)
T ... film thickness

Claims (23)

To recycle a used metal working tool provided with a cermet base material composed of a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride and titanium carbonitride Reprocessing method,
A cleaning step of cleaning the surface of the cermet substrate;
After the cleaning step is completed, a surface-coated cermet member that forms a metal processing tool after reprocessing is obtained by forming an oxidation resistant film composed of a composite oxide containing titanium on the surface of the cermet base material. Including an oxidation resistant film forming step,
The washing step includes
Alkaline washing treatment for washing the cermet base material with an alkaline aqueous solution;
A first water washing treatment for washing the cermet base material with hot water after the alkali washing treatment is completed;
After the first water washing treatment is completed, the metal processing tool reprocessing method is characterized in that after the moisture on the surface of the cermet base material is blown off by air blow, the first drying treatment is naturally performed. .   The metal processing tool reprocessing method according to claim 1, wherein, in the cleaning step, neutralization treatment with an acidic aqueous solution is performed after the alkali cleaning treatment and before the first water washing treatment.   The metal processing tool reprocessing method according to claim 1 or 2, wherein in the cleaning step, after the first drying process is performed, a surface polishing process is performed to polish the surface of the cermet base material with a polishing tool.   The metal processing tool reprocessing method according to claim 3, wherein after the surface polishing process is performed in the cleaning step, an organic solvent cleaning process for cleaning the cermet base material is performed with an organic solvent.   5. The metal processing tool reprocessing method according to claim 4, wherein in the cleaning step, after the organic solvent cleaning process is performed, a second water cleaning process of cleaning the cermet base material with hot water is performed.   6. The metal processing according to claim 5, wherein, in the cleaning step, after the second water washing process is performed, a second drying process is performed in which the moisture of the cermet base material is blown off by air blow and then naturally dried. Tool reprocessing method.   The said titanium compound is a reprocessing method of the metal working tool of any one of Claims 1-6 comprised with a titanium carbonitride.   The oxidation resistant film is formed by applying a treatment liquid containing a metal salt that reacts with a titanium compound on the surface of the cermet base material to form the composite oxide, and then heating the cermet base material. The reprocessing method of the metal working tool of any one of Claims 1-7.   The metal processing tool reprocessing method according to claim 8, wherein an oxidation treatment is performed on the cermet base material in advance before applying the treatment liquid.   The metal processing tool reprocessing method according to claim 1, wherein the oxidation-resistant film is made of a perovskite complex oxide.   The method for reprocessing a metal working tool according to claim 10, wherein the oxidation resistant film is formed by applying a treatment liquid containing an alkaline earth metal compound to the cermet substrate and then heating the cermet substrate.   The method for reprocessing a metal working tool according to any one of claims 1 to 9, wherein the oxidation resistant film is made of an ilmenite complex oxide.   The method for reprocessing a metal working tool according to claim 12, wherein the oxidation resistant film is formed by applying a treatment liquid containing a transition metal compound of an iron group divalent ion to the cermet base material and then heating the cermet base material. .   The said oxidation-resistant film is a reprocessing method of the metal working tool of any one of Claims 1-9 comprised with a spinel type complex oxide.   The method of reprocessing a metal working tool according to claim 14, wherein the oxidation resistant film is formed by applying a treatment liquid containing a magnesium compound or a cobalt compound to the cermet base material and then heating the cermet base material.   The method for reprocessing a metal working tool according to any one of claims 1 to 15, wherein the oxidation-resistant film has a thickness of 0.5 µm or less.   The method for reprocessing a metal working tool according to claim 1, wherein the composite oxide has a crystal structure in which oxygen ions are closely packed. An extrusion die for extruding an extruded material,
An extrusion die formed by a reprocessed metal working tool obtained by the reprocessing method according to claim 1. An extrusion method in which an extruded material is extruded by an extrusion die subjected to preheating,
While using the extrusion die according to claim 18, as the extrusion die,
An extrusion processing method, wherein after the extrusion molding is started, the oxidation resistant film of the extrusion die is peeled off by a flowing extruded material. Surface coating in which an oxidation-resistant film is formed on the surface of a cermet base material composed of a sintered body mainly composed of at least one titanium compound of titanium carbide, titanium nitride and titanium carbonitride. A method of manufacturing a cermet member,
A cleaning step of cleaning the surface of the cermet substrate;
After the cleaning step is completed, forming the oxidation-resistant film composed of a composite oxide containing titanium on the surface of the cermet, and obtaining the surface-coated cermet member,
The washing step includes
An alkali cleaning treatment for cleaning the surface of the used metal working tool with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the metal processing tool with hot water,
After the water washing treatment is completed, the moisture on the surface of the metal working tool is blown off by air blow, and then a drying treatment is performed to dry naturally.
The oxidation resistant film forming step includes:
A treatment liquid coating treatment for coating a treatment liquid containing a metal salt that reacts with the titanium compound on the surface of the cermet base material to form a composite oxide on the surface of the cermet base material,
A method for producing a surface-coated cermet member, wherein a heat treatment for forming an oxidation-resistant film is performed by heating after the coating. Surface coating in which an oxidation-resistant film is formed on the surface of a cermet base material composed of a sintered body mainly composed of at least one titanium compound of titanium carbide, titanium nitride and titanium carbonitride. A method of manufacturing a cermet member,
A cleaning step of cleaning the surface of the cermet substrate;
An oxidation resistant film forming step of obtaining the surface-coated cermet member by forming the oxidation resistant film composed of a composite oxide containing titanium on the surface of the cermet after the cleaning step is completed;
The washing step includes
Alkaline washing treatment for washing the cermet base material with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the cermet base material with hot water,
After the water washing treatment is completed, the moisture on the surface of the cermet base material is blown off by air blow, and then a drying treatment for natural drying is performed.
The oxidation resistant film forming step includes:
An oxidation treatment for oxidizing the cermet substrate by heating;
A treatment liquid coating treatment for coating a treatment liquid containing a metal salt that reacts with the titanium compound on the surface of the cermet base material to form a composite oxide on the surface of the cermet base material subjected to the oxidation treatment;
A method for producing a surface-coated cermet member, wherein a heat treatment for forming an oxidation-resistant film is performed by heating after the coating. The surface of a cermet substrate composed of a sintered body containing at least one titanium compound as a main component of hard phase among titanium carbide, titanium nitride and titanium carbonitride is composed of a composite oxide containing titanium. A method for forming an oxidation resistant film of a cermet base material for forming an oxidation resistant film comprising:
Before forming the oxidation-resistant film on the cermet base material, including a cleaning step of cleaning the surface of the cermet base material in advance.
The washing step includes
Alkaline washing treatment for washing the cermet base material with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the cermet base material with hot water,
A method for forming an oxidation-resistant film on a cermet base material, wherein after the water washing treatment is completed, moisture on the surface of the cermet base material is blown off by air blow, followed by a drying process of natural drying. An anti-oxidation method for a titanium-based sintered body for preventing oxidation in a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride, and titanium carbonitride,
A cleaning step of cleaning the surface of the sintered body;
After the cleaning step is completed, an oxidation resistant film forming step of forming an oxidation resistant film composed of a composite oxide containing titanium on the surface of the sintered body,
The washing step includes
Alkaline washing treatment for washing the sintered body with an alkaline aqueous solution;
After the alkali cleaning treatment is completed, a water washing treatment for washing the sintered body with hot water,
An anti-oxidation method for a titanium-based sintered body, characterized in that after the water washing treatment is completed, moisture on the surface of the sintered body is blown off by air blow, and then a drying treatment is performed for natural drying.

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