JP2019119914A - Resin zirconium alloy joined body and production method thereof - Google Patents

Abstract

To provide a resin zirconium alloy joined body with a bonding strength, and a production method thereof.SOLUTION: A production method of a resin zirconium alloy joined body of the present invention comprises: a degreasing process for cleaning a zirconium member with an alkaline solution; an acid treatment process for cleaning the zirconium member with an acidic solution; an activation treatment process in which the zirconium member is immersed in the alkaline solution and a constant voltage is applied to an electrode; a process in which an anodic oxide film is formed on the zirconium member with a film thickness of 50-3000 nm while a prescribed current density is applied in a solution including an alkaline triazinethiol derivative using the zirconium member as an anode; a washing process in which the zirconium member on which the anodic oxide film is formed is washed with water; and a process in which a thermoplastic resin is inserted to mold into the zirconium member on which the anodic oxide film is formed.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin-zirconium alloy bonded body and a method of manufacturing the same, and more particularly, to a resin-zirconium alloy bonded body capable of strongly bonding a resin member and a zirconium member and a method of manufacturing the same.

  Weight reduction of components can be performed by making a metal member into the joined body of a metal member and a resin member as an example. Patent Document 1 discloses, as a technique for bonding a resin member and a metal member, an electro-chemical surface treatment method of forming a film containing triazine thiol (sulfur organic compound) on the surface of the metal member. Examples of metals include copper, nickel, aluminum, iron, cobalt, tin and stainless steel. By forming the coating on the metal surface, the bonding strength with the resin member can be improved.

  However, there is no specific disclosure on forming a film of triazine thiol on a member made of zirconium alloy and bonding a resin member thereon to form a resin-metal bonded body to obtain a sufficient bonding strength.

Tokuhei 5-51671

  An object of the present invention is to provide a resin-zirconium alloy bonded body capable of improving the bonding strength between a resin member and a zirconium member, and to provide a method for producing a resin-zirconium alloy bonded body having good bonding strength.

  The resin zirconium alloy joined body according to the present invention is a resin zirconium alloy joined body formed by joining a zirconium member made of zirconium alloy and a thermoplastic resin member, wherein the zirconium member and the resin member have a film thickness Are bonded by an anodized film of 50 to 3000 nm.

  Another resin zirconium alloy joined body according to the present invention is a resin zirconium alloy joined body formed by joining a zirconium member and a thermoplastic resin member, wherein the zirconium alloy member and the resin member have a thickness of 50 to 50 nm. It is characterized in that it is bonded by an anodic oxidation film in which triazine thiol of 3000 nm is present internally and externally.

  The anodic oxide film is, by weight, 1 to 60% of oxygen (O), 1 to 90% of zirconium (Zr), 10% or less of aluminum (Al), 20% or less of nickel (Ni), copper 20% or less of Cu), 1% or less of silicon (Si), 1% or less of yttrium (Y), 1% or less of niobium (Nb), and 1% or less of fluorine (F) I assume.

  The method for producing a resin-zirconium alloy joined body according to the present invention is a method for producing a resin-zirconium alloy joined body, comprising: a degreasing step of cleaning a zirconium member made of a zirconium alloy with an alkaline solution; The acid treatment step of washing the member with an acidic solution, the activation treatment step of applying a constant voltage to the electrode by immersing the zirconium member in an alkaline solution after the acid treatment step, and using the zirconium member as an anode Forming an anodic oxide film having a thickness of 50 to 3000 nm on the zirconium member by applying a current density of 0.5 A / dm 2 or more and less than 5 A / dm 2 in an alkaline solution at 90 ° C .; A water-washing step of washing the zirconium member having the oxide film formed thereon with water at 5 ° C. or more and less than 60 ° C., and after the water-washing step A step of insert molding a thermoplastic resin on the zirconium member having the anodized film formed thereon, and the zirconium member and a resin member molded of a thermoplastic resin are joined by the anodized film It is characterized by

  Another method for producing a resin-zirconium alloy joined body according to the present invention is a method for producing a resin-zirconium alloy joined body, comprising: a degreasing step of cleaning a zirconium member made of a zirconium alloy with an alkaline solution; An acid treatment step of washing the zirconium member with an acidic solution, an activation treatment step of applying a constant voltage to the electrode by immersing the zirconium member in an alkaline solution after the acid treatment step, and using the zirconium member as an anode, A current density of 0.5 A / dm 2 or more and 5 A / dm 2 or less is applied in a solution containing an alkaline triazine thiol derivative at 90 ° C. to form an anodized film having a thickness of 50 to 3000 nm on the zirconium member And washing the zirconium member having the anodized film formed thereon with water at 5 ° C. or more and less than 60 ° C. A step of washing with water, and a step of insert molding a thermoplastic resin on the zirconium member on which the anodic oxidation film has been formed after the step of water washing, and the zirconium member, and a resin member molded of a thermoplastic resin Are bonded by the anodized film.

In the resin-zirconium alloy joined body according to the present invention, since the anodic oxide film having a thickness of 50 to 3000 nm is formed on the surface of the zirconium member in advance, the resin member and the zirconium member can be joined well and the bonding strength can be 30 MPa or more . The airtightness between the resin member and the zirconium member can be 10 ^-9 Pa · m ³ / s or less in a leak test using a helium leak. In addition, waterproofness can be secured.

Another resin-zirconium alloy joined body according to the present invention has an anodized film in which triazine thiol having a thickness of 50 to 3000 nm is present inside and outside on the surface of the zirconium member in advance. It can be joined well. The bonding strength can be 30 MPa or more. The airtightness between the resin member and the zirconium member can be 10 ^-9 Pa · m ³ / s or less in a leak test using a helium leak.

  The anodic oxide film is, by weight, 1 to 60% of oxygen (O), 1 to 90% of zirconium (Zr), 10% or less of aluminum (Al), 20% or less of nickel (Ni), copper 20% or less of Cu), 1% or less of silicon (Si), 1% or less of yttrium (Y), 1% or less of niobium (Nb), 1% or less of fluorine (F) The member and the zirconium member can be joined well.

According to the method for producing a resin-zirconium alloy joined body according to the present invention, (a) immersion, degreasing step for removing fats from the surface of the zirconium alloy member, (b) acid treatment step, and (c) immersion in an alkaline solution And (d) forming an anodic oxide film in an alkaline solution using the zirconium member as an anode, and (e) forming the zirconium member after forming the anodic oxide film. Since the water washing step of washing with water and the insert step of (f) insert molding the thermoplastic resin and bonding to the zirconium member are provided, the resin member and the zirconium member can be favorably bonded, and the bonding strength is 30 MPa or more The air tightness can be less than 10 ^-9 Pam ³ / s in a leak test using a helium leak.

According to the manufacturing method of another resin-zirconium alloy joined body according to the present invention, (a) a degreasing step for removing fats from the surface of the zirconium alloy member by immersion, (b) an acid treatment step, (c) an alkaline solution Step of activation in which constant voltage is applied and (d) a zirconium member is used as an anode, and an oxide film forming step (referred to as TRI electrolytic step) of forming an anodic oxide film in an alkaline solution containing triazine thiol derivative And (e) a water washing step of washing the zirconium member with water after forming the anodized film, and (f) an insert step of insert molding the thermoplastic resin and bonding it to the zirconium member, the resin member And the bonding strength of the zirconium member can be 30 MPa or more, and the airtightness can be 10 ^-9 Pam ³ / s or less in a leak test using a helium leak.

It is a flowchart which shows the manufacturing method of the resin zirconium alloy joined body by this invention. It is a figure which shows the shape of a zirconium member. (A) is a front view, (B) is a right side view, and (C) is a perspective view. It is a table | surface which shows the kind and component of a zirconium alloy. It is a photograph of the suspension jig of a zirconium member. It is the photograph by which the hanging jig was hung down to the degreasing tank. It is the photograph by which the hanging jig was hung down to the activation process tank. It is a photograph of a TRI electrolytic processing tank. It is a photograph which shows the cross section of an anodic oxidation film. It is a photograph which shows the cross section of an anodic oxidation film. They are a photograph (left side) of a zirconium member and a photograph (right side) of the test body for a tension test manufactured by the manufacturing method shown in FIG. It is a table showing the tensile strength of the resin zirconium alloy joined body. It is a table | surface which shows the tensile strength after a reliability test. It is a table | surface which shows the tensile strength after a reliability test. It is an external appearance (photograph) of the test body for an airtight test. It is a table | surface which shows the result of an airtight test. It is the surface photograph and component analysis table after TRI electrolytic treatment of a zirconium member (a zirconium alloy uses type 1). It is the surface photograph and component analysis table after TRI electrolytic treatment of a zirconium member (zirconium alloy uses type 2). It is the surface photograph and component-analysis table after a zirconium member (a zirconium alloy uses type 3) TRI electrolytic processing. It is a table | surface which shows the joint strength of the resin zirconium alloy joined body in the case where triazine thiol is added, and the case where it is not added.

  Hereinafter, a resin-zirconium alloy joined body according to the present invention and a method for producing the same will be described in detail with reference to the drawings.

FIG. 1 is a flow chart showing a method of producing a resin-zirconium alloy joined body according to the present invention. The resin-zirconium alloy joined body is formed by joining a zirconium member and a resin member and integrally forming them. The formation of the resin-zirconium alloy joined body is performed in the following six steps s1 to s6. In the degreasing step (s1), a cationic surfactant is added to an aqueous solution of alkaline series of NAOH, KOH or NA ₂ CO ₃ , and the zirconium member 1 is immersed for 1 to 10 minutes. The temperature of the aqueous solution is in the range of normal temperature to 80 ° C. Thus, the oil on the surface of the zirconium member 1 is removed. The zirconium member 1 is a plate-like member and made of a zirconium alloy.

  Next, in the acid treatment step (s2), 5 to 50% phosphoric acid, 1 to 20% sulfuric acid or phosphoric acid, 1 to 5% ethylene glycol, 1 to 5% glycerin, trace amount of EDTA (ethylenediaminetetraacetic acid) by weight Immerse the zirconium member 1 in an aqueous solution of a slight amount of non-benol ethoxylate for 1 to 10 minutes. The temperature of the aqueous solution is in the range of normal temperature to 50 ° C. Thus, the surface of the zirconium member 1 is cleaned to remove the oxide film and the like.

  In the activation step (s3), a small amount of EDTA (ethylenediaminetetraacetic acid) is added to an aqueous solution of phosphoric acid or sulfuric acid 1 to 5% by weight, and the zirconium member 1 is immersed in the solution for 1 to 10 minutes. Alternatively, a constant voltage of 0.2 to 5 V is applied to the cathode. The temperature of the aqueous solution is normal temperature to 50 ° C. Pulsed or DC voltage is applied to the electrodes. Sonicate also for 100 to 2000 watts at 50 Hz for 1 to 10 minutes simultaneously.

The oxide film forming step (s4) is referred to as a TRI electrolytic step. The zirconium member 1 is connected as an anode. 1% by weight phosphoric acid or sulfuric acid, 1 to 5% aluminum sulfate, trace addition of EDTA (ethylenediaminetetraacetic acid), 1 to 3% oxalic acid or citric acid, trace addition of triazine thiol, zirconium member 1 And apply a constant current density of 1 to 20 A / dm ² between the anode and the cathode. The temperature of the solution is normal temperature to 80 ° C. A voltage of 1 to 20 V is applied between the anode and the cathode. By the electrolysis for 1 to 40 minutes, the anodized film 4 containing triazine thiol and having a film thickness of 50 to 3000 nm is formed on the surface of the zirconium member. A porous film can be formed. In addition, an oxide film formation process (s4) can also be performed with the aqueous solution which does not add triazine thiol.

  The water washing step (s5) is a step of washing the zirconium member 1 having the anodized film formed on the surface, with water having a water temperature of 5 ° C to 60 ° C. In addition, let it dry after washing with water. In the insert molding step (s6), the zirconium member 1 on which the anodized film is formed is loaded into a mold, a thermoplastic resin to be the resin member 2 is injected, and the resin member 2 and the zirconium member 1 are joined to form resin zirconium An alloy joined body 3 is formed.

  FIG. 2 is a view showing the shape of the zirconium member 1. (A) is a front view, (B) is a right side view, and (C) is a perspective view. a is a hole for tensile test with a diameter of 4 mm. f is 3 mm in thickness. Vertical x horizontal is a plate of 40 mm x 12 mm, b is 12 mm and e is 40 mm. c is 6 mm and d is 5 mm.

  FIG. 3 is a table showing the types and components of the zirconium alloy. Type 1 has high copper (Cu) content to provide corrosion resistance, and yttrium (Y) is added to improve strength. In types 2 and 3, the content of copper (Cu) is reduced, and niobium (Nb) improves corrosion resistance and heat resistance. Although the zirconium alloy of type 1 is used as the zirconium member 1 in the present embodiment, the present invention is not limited to this, and types 2 and 3 may be used.

FIG. 4 is a photograph of the hanging jig 7 to which the zirconium member 1 can be attached. The hanging jig 7 has 5 × 2 rows of hooks lined up, and ten zirconium members 1 can be mounted thereon. FIG. 5: is the photograph by which the hanging jig 7 was hung down to the degreasing tank. The degreasing tank is filled with an aqueous solution prepared by adding a cationic surfactant to NAOH, KOH, or NA ₂ CO ₃ . FIG. 6 is a photograph in which the hanging jig 7 is hung in the activation treatment tank. FIG. 7 is a photograph of a TRI electrolytic treatment tank. Several electrodes are prepared in a tank.

FIG. 8 is a photograph showing a cross section of the anodized film. On the surface of the anodized film 4, in (A), the anodized film 4 with a thickness of 96 nm is formed. In (B), the anodic oxide film 4 with a thickness of 171 nm is formed.
FIG. 9 is a photograph showing a cross section of the anodized film. The thickness of the anodized film 4 can be read at 800 nm, 556 nm, 758 nm, and 950 nm. The anodized film 4 can have a thickness of 50 nm to 3000 nm (= 3.0 μm).

FIG. 10 is a photograph of the zirconium member (left side) and a photograph of the test sample for tensile test manufactured by the manufacturing method shown in FIG. 1 (right side). As shown in FIG. 10, the end faces of 12 mm × 3 mm (= 36 mm ² ) of the zirconium member 1 and the resin member 2 are joined. The test body is indicated by symbol 3 (3a). That is, it is a test body 3a for a tensile test. The resin-zirconium alloy bonded body 3 is obtained by integrally molding the resin member 2 on the zirconium member 1 by insert molding. In the insert molding, the zirconium member 1 is loaded in a mold (not shown), and the zirconium member 1 and the resin member 2 are integrally molded by press-fitting a thermoplastic resin. As the thermoplastic resin, polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS) can be used.

FIG. 11 is a table showing the tensile strength of the resin-zirconium alloy joined body 3 (3a). As shown in the PPS column on the right side of the table, the tensile strengths of the five test specimens were 33.9 MPa to 47.2 MPa from the top to the bottom. This value is a value when the bonding area is 36 mm ² (= 12 mm × 3 mm). As shown in the PBT column on the right side of the table, the tensile strengths of the five test specimens were 38.1 MPa to 31.9 MPa from the top to the bottom. According to this, with a bonding area of 36 mm ² , a strength of about 30 MPa can be secured. The left side of the table shows the thickness of the zirconium member 1 measured for reference, and it can be seen that the thickness of each of the five samples decreases by 3 to 5 μm.

  FIG. 12 is a table showing the tensile strength after the reliability test. The case where the resin member 2 of the resin zirconium alloy joined body 3 (3a) is polyphenylene sulfide (PPS) is shown. (1) High-Temperature High-Humidity Test 1 was conducted after the test at a temperature of 80 ° C. and a humidity of 95% for a test time of 72 hours. (2) High-Temperature High-Humidity Test 2 was conducted after the test at a temperature of 80 ° C. and a humidity of 95% with a test time of 200 hours. (3) The salt spray test was measured 72 hours after salt spray. (4) The thermal shock test was performed after changing the temperature between minus 40 ° C. and 80 ° C. every 30 minutes and repeating 150 cycles. The left end of the table shows the tensile strength of the resin-zirconium alloy joined body 3 (3a) before the reliability test, which can grasp the tendency of 10 test pieces and shows a value of 31.2 MPa to 45.2 MPa . With 10 pieces × 4 sets of similarly manufactured specimens, the high temperature and high humidity test (after 72 h), the high temperature and high humidity test (after 200 h), the salt spray test and the thermal shock test were carried out, respectively, and tensile strength Was measured. The measured values are as shown in FIG.

  FIG. 13 is a table showing tensile strengths after the reliability test. The case where the resin member 2 of the resin zirconium alloy joined body 3 (3a) is polybutylene terephthalate (PBT) is shown. (1) High-Temperature High-Humidity Test 1 was conducted after the test at a temperature of 80 ° C. and a humidity of 95% for a test time of 72 hours. (2) High-Temperature High-Humidity Test 2 was conducted after the test at a temperature of 80 ° C. and a humidity of 95% with a test time of 200 hours. (3) The salt spray test was measured 72 hours after salt spray. (4) The thermal shock test was performed after changing the temperature between minus 40 ° C. and 80 ° C. every 30 minutes and repeating 150 cycles. The tensile strength was measured by performing a high temperature and high humidity test (after 72 h), a high temperature and high humidity test (after 200 h), a salt spray test, and a thermal shock test on 10 pieces of the test body × 4 groups. The measured values are as shown in FIG.

  FIG. 14 is an appearance (photograph) of a test body for air tightness test. The test body is shown by resin zirconium alloy joined body 3 (3b). In the test body 3b for the air tightness test, the zirconium member 1 penetrates the disc-shaped resin member 2 and is integrally joined. A cylindrical container is loaded with the test body 3b for air tightness test, helium gas is blown to one side from which the zirconium member 1 protrudes, the other side from which the zirconium member 1 protrudes is evacuated, and helium gas does not leak Find out

FIG. 15 is a table showing the results of the airtightness test. If the amount of vacuum evacuation is increased or decreased, the amount of leaked helium (He) is also increased or decreased, but under this condition, the amount of leakage can be made 1 × 10 ⁻⁹ Pam ³ / s or less in both of the samples 1 and 2.

  FIG. 16 is a surface photograph and a component analysis table of a zirconium member (a zirconium alloy uses type 1) after TRI electrolytic treatment. Type 1 zirconium alloys are shown in FIG. The surface is porous and uneven. According to the composition table of the anodized film, by weight%, Zr is 62.34%, O is 21.33%, and zirconium oxide (ZrO) is formed.

  FIG. 17 is a surface photograph and a component analysis table of a zirconium member (a zirconium alloy uses type 2) after TRI electrolytic treatment. Type 2 zirconium alloys are shown in FIG. The surface is porous and has less irregularities than Type 1. According to the composition table of the anodized film, it is 62.05% of Zr and 12.53% of O by weight, and zirconium oxide (ZrO) is formed.

  FIG. 18 is a surface photograph and a component analysis table of a zirconium member (a zirconium alloy uses type 3) after TRI electrolytic treatment. Type 3 zirconium alloys are shown in FIG. The surface is porous and has less irregularities than Type 2. According to the composition table of the anodized film, Zr is 63.77% and O is 12.38% by weight, and zirconium oxide (ZrO) is formed.

  FIG. 19 is a table showing the bonding strength of a resin-zirconium alloy joined body with and without triazine thiol. In the TRI electrolytic process of FIG. 1, an anodic oxide film was formed without adding triazine thiol to the aqueous solution, and a resin zirconium alloy joined body 3 (3a) was manufactured. On the other hand, triazine thiol was added to the aqueous solution in the TRI electrolysis step of FIG. 1 to form an anodic oxide film, and a resin zirconium alloy joined body 3 (3a) was manufactured. The bonding strengths of each of the five produced resin-zirconium alloy bonded bodies were compared. The numerical values are slightly better when triazinethiol is added. However, even if it does not add triazine thiol, it can be said that it can fully use it.

  The resin-zirconium alloy joined body of the present invention and the method for producing the same are such that a member made of a zirconium alloy and a resin member are integrally joined and joined, and there is a joint strength, which is suitable for weight reduction of parts.

DESCRIPTION OF SYMBOLS 1 zirconium member 2 resin member 3 resin zirconium alloy joined body 3 a test body for tensile test 3 b test body for air tightness test 4 anodized film 7 hanging jig s1 to s6 each process of manufacturing method

Claims (5)

A resin-zirconium alloy joined body obtained by joining a zirconium member made of a zirconium alloy and a thermoplastic resin member,
A resin-zirconium alloy joined body, wherein the zirconium member and the resin member are joined by an anodized film having a thickness of 50 to 3000 nm. A resin-zirconium alloy joined body obtained by joining a zirconium member made of a zirconium alloy and a thermoplastic resin member,
A resin-zirconium alloy joined body, wherein the zirconium member and the resin member are joined by an anodic oxide film in which triazine thiol having a thickness of 50 to 3000 nm is present inside and outside.   The anodic oxide film is, by weight, 1 to 60% of oxygen (O), 1 to 90% of zirconium (Zr), 10% or less of aluminum (Al), 20% or less of nickel (Ni), copper 20% or less of Cu), 1% or less of silicon (Si), 1% or less of yttrium (Y), 1% or less of niobium (Nb), and 1% or less of fluorine (F) The resin zirconium alloy joined body according to claim 1 or 2. A manufacturing method of producing a resin-zirconium alloy joined body,
A degreasing step of cleaning a zirconium member made of a zirconium alloy with an alkaline solution;
After the acid treatment step, the zirconium member is immersed in an alkaline solution to apply a constant voltage to the electrode, and an activation treatment step;
An acid treatment step of washing the zirconium member with an acidic solution after the degreasing step;
The zirconium member is used as an anode, and a current density of 0.5 A / dm 2 or more and 5 A / dm 2 or less is applied in an alkaline solution at 20 to 90 ° C. Forming a film;
A water washing step of washing the zirconium member having the anodized film formed thereon with water at 5 ° C. or more and less than 60 ° C .;
Insert molding a thermoplastic resin on the zirconium member on which the anodized film has been formed after the water washing step;
A method for producing a resin-zirconium alloy joined body, characterized in that the zirconium member and a resin member formed of a thermoplastic resin are joined by the anodized film. A manufacturing method of producing a resin-zirconium alloy joined body,
A degreasing step of cleaning a zirconium member made of a zirconium alloy with an alkaline solution;
An acid treatment step of washing the zirconium member with an acidic solution after the degreasing step;
After the acid treatment step, the zirconium member is immersed in an alkaline solution to apply a constant voltage to the electrode, and an activation treatment step;
The zirconium member is used as an anode, and a current density of 0.5 A / dm 2 or more and 5 A / dm 2 or less is applied in a solution containing an alkaline triazine thiol derivative at 20 to 90 ° C. Forming an anodic oxide film of ̃3000 nm,
A water washing step of washing the zirconium member having the anodized film formed thereon with water at 5 ° C. or more and less than 60 ° C .;
Insert molding a thermoplastic resin on the zirconium member on which the anodized film has been formed after the water washing step;
A method for producing a resin-zirconium alloy joined body, characterized in that the zirconium member and a resin member formed of a thermoplastic resin are joined by the anodized film.

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