KR20200145893A - Titanium clad material and method for manufacturing the same - Google Patents

Abstract

According to an embodiment of the present invention, a clad material comprises: a titanium metal plate; a different metal plate joined to at least one surface of the titanium metal plate; and a plating layer interposed between the titanium metal plate and the different metal plate. The present invention omits an explosion process or a vacuum process by a method of electroplating the titanium metal plate, continuously performs a manufacturing process other than joining, effectively prevents the formation of a passive film created during the manufacturing process after etching, allows manufacture without oxidation in a high-temperature oxidative atmosphere, and simplifies the manufacturing process to markedly reduce product costs and production expenses.

Description

Titanium cladding material and its manufacturing method TECHNICAL FIELD [TITANIUM CLAD MATERIAL AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a titanium clad material and a method of manufacturing the same.

The cladding material is a material manufactured to realize the advantages of each metal by combining various metals by bonding technology. The cladding material can be manufactured in various ways depending on the properties of the metal to be used for bonding and the desired shape and physical properties of the material.

Although titanium has excellent corrosion resistance, it is characterized by a high price compared to general materials. Accordingly, in order to increase the usability while lowering the unit price, a method of bonding with dissimilar metals other than titanium and utilizing it as a cladding material has been attempted.

However, since titanium is easily oxidized in the atmosphere to form a passivation film (oxide film) on the surface, the passivation film may be formed again by contact with the atmosphere during the manufacturing process even after the passivation film is removed by etching. In this case, the passivation film not only lowers the bonding strength between titanium and dissimilar metals, but also creates an intermetallic compound at the interface at a high bonding temperature, resulting in poor quality of the cladding material.

In general, cladding materials using titanium are widely known in manufacturing methods such as explosion welding method in which two metal plates are bonded under pressure generated by explosion of gunpowder, and vacuum bonding method in which the formation of a passivation film is prevented in a vacuum atmosphere and bonded at high temperature. However, this method requires complex equipment and expensive equipment to provide a vacuum or explosive environment. In addition, since bonding by vacuum or explosion is performed by a separate process, it is difficult to continuously perform a manufacturing process other than the bonding process, so that productivity and economy are lowered.

In order to solve this problem, as an example, a method of rolling-joining in a manner in which only dissimilar metals of the cladding material are heated and titanium is not heated has been proposed. In this case, the passivation film generated during the manufacturing process may be partially removed by the bonding pressure, but it is difficult to prevent the passivation film or the intermetallic compound generated by the high temperature instantaneously transferred when the heated dissimilar metal and titanium are bonded.

As another example, a method of laminating a metal foil of a metal having excellent corrosion resistance such as niobium or vanadium between titanium and dissimilar metals, and bonding at a high temperature is also proposed. In this case, it is difficult to realize economical efficiency to the extent that it is commercially usable by metal foils such as niobium and vanadium, which are metals having a high unit cost, and it is difficult to uniformly deposit the metal foil in a desired shape.

Therefore, in recent years, while replacing the explosion process or vacuum process including high-risk and expensive equipment, it is possible to continuously perform with manufacturing processes other than bonding, The demand is increasing.

The prior art of the present invention is mentioned in Korean Patent Publication No. 10-2006-0026263 and US Patent No. 4,612,259.

One object of the present invention is to provide a titanium clad material having excellent interfacial bonding strength and a method of manufacturing the same, which can be continuously performed with manufacturing processes other than bonding while omitting the explosion process or vacuum process.

Another object of the present invention is to effectively prevent the formation of a passivation film that occurs during the manufacturing process after etching, and can be manufactured without oxidation in a high-temperature oxidizing atmosphere, and the manufacturing process is simplified, thereby remarkably reducing product cost and production cost. It is to provide a titanium cladding material and a method of manufacturing the same.

Another object of the present invention is to provide a titanium clad material having excellent strength, bonding force, and drawing ratio of a material, and reduced formation of intermetallic compounds at the interface, and a method of manufacturing the same.

An embodiment of the present invention is a titanium metal plate; A dissimilar metal plate bonded to at least one surface of the titanium metal plate; And a plating layer interposed between the titanium metal plate and the dissimilar metal plate. It relates to a cladding material containing.

Another embodiment of the present invention is a pretreatment step of removing the oxide film of the titanium metal plate; Forming a plating layer by performing electroplating on the surface of the titanium metal plate from which the oxide film has been removed; Heat-treating the titanium metal plate and the dissimilar metal plate on which the plating layer is formed at a temperature of 200°C to 400°C, respectively; Laminating the heat-treated dissimilar metal plate on at least one surface of the titanium metal plate on which the plating layer is formed, and then rolling the laminate at a reduction ratio of 20% to 30%; And annealing heat treatment of the rolled laminate at 250°C to 500°C. It relates to a clad material manufacturing method comprising a.

The pretreatment step may be to treat the titanium metal plate with a mixture of at least one of NaF and NaHF _{2 and at} least one of hydrochloric acid, nitric acid and acetic acid.

The heat treatment temperature of the annealing heat treatment step may be 400°C to 500°C.

In the above embodiments, the plating layer may be a nickel plating layer.

In the above embodiments, the dissimilar metal plate may include one or more of aluminum, stainless steel, copper, high carbon steel, nickel alloy, and lead alloy.

In the above embodiments, the thickness ratio of the titanium metal plate and the dissimilar metal metal plate may be 1: 1.5 to 2.5.

In the above embodiments, the plating layer may be formed to a thickness of 0.1 μm to 5 μm.

In the present invention, while omitting the explosion process or the vacuum process, it is possible to continuously perform with a manufacturing process other than bonding, has excellent interfacial bonding, and effectively prevents the formation of a passivation film occurring during the manufacturing process after etching, It can be manufactured without oxidation in an oxidizing atmosphere, the manufacturing process is simplified, and the product unit cost and production cost can be significantly reduced, the strength, bonding strength and drawing ratio of the material are excellent, and the formation of intermetallic compounds at the interface is reduced, It provides a titanium cladding material having anti-embrittlement ability and a method for producing the same.

1 is a schematic cross-sectional view of a cladding material according to an embodiment of the present invention.
2 is a schematic cross-sectional view of a cladding material according to another embodiment of the present invention.
3 is a schematic diagram of an exemplary method of manufacturing a cladding material of the present invention.
Figure 4 is a schematic diagram of the equipment used to manufacture the cladding material in Example 1 of the present invention.
5 shows the results of evaluating the plating properties of Example 1 of the present invention.
6 shows the results of component analysis and evaluation of Example 1 of the present invention.
7 shows the result of evaluating Φ85 cupping of Example 1 of the present invention.
8 shows the result of Φ90 cupping evaluation of Example 1 of the present invention.
9 shows the result of evaluating Φ95 cupping of Example 1 of the present invention.

An embodiment of the present invention is a titanium metal plate; A dissimilar metal plate bonded to at least one surface of the titanium metal plate; And a plating layer interposed between the titanium metal plate and the dissimilar metal plate. It relates to a cladding material containing.

In the present invention, through the method of electroplating a titanium metal plate, it is possible to continuously perform a manufacturing process other than bonding while omitting an explosion process or a vacuum process, and effectively prevent the formation of a passivation film that occurs during the manufacturing process after etching. Yet, it can be manufactured without oxidation in a high-temperature oxidizing atmosphere, and the manufacturing process is simplified, and product unit cost and production cost can be significantly reduced.

In addition, through this, the interfacial bonding strength, strength, bonding strength, and drawing ratio of the cladding material of the titanium clad material can be realized to an excellent degree, the formation of intermetallic compounds at the interface can be reduced, and embrittlement prevention ability can be realized.

Specifically, the titanium metal plate may be a metal steel plate containing 99% by weight or more of titanium (Ti), more specifically 99% by weight to 99.99% by weight, and even more specifically 99% by weight to 99.96% by weight. In this case, while sufficiently utilizing the corrosion resistance of titanium, the interfacial bonding strength, strength, bonding strength, and drawing ratio of the cladding material may be further improved.

Specifically, the titanium metal plate is an oxygen (O) component other than titanium 0.018% by weight to 0.9% by weight or less; Nitrogen (N) 0.003% by weight or more to 0.15% by weight or less; 0.0015% by weight or more to 0.075% by weight or less of hydrogen (H); Iron (Fe) 0.01% by weight or more to 0.8% by weight or less; And inevitable impurities of the remainder. In this case, the inevitable impurities may include at least one of aluminum (Al), vanadium (V), and palladium (pd). In this case, while sufficiently utilizing the corrosion resistance of titanium, the interfacial bonding strength, strength, bonding strength, and drawing ratio of the cladding material may be further improved.

In one embodiment, the titanium metal plate is titanium (Ti) 99.48% by weight, oxygen (O) 0.18% by weight, nitrogen (N) 0.03% by weight, hydrogen 0.015% by weight, iron (Fe) 0.20% by weight and inevitable impurities of the balance It may be made of. In this case, while sufficiently utilizing the corrosion resistance of titanium, the interfacial bonding strength, strength, bonding strength, and drawing ratio of the cladding material may be further improved.

The titanium metal plate may have a thickness of 0.1 mm to 20 mm, specifically 0.1 mm to 10 mm, and more specifically 1 mm to 5 mm. Within the above range, the cladding material may further improve interfacial bonding strength, strength, bonding force, and a drawing ratio of the cladding material while implementing excellent corrosion resistance and strength.

The dissimilar metal plate may include at least one of aluminum, stainless steel, copper, carbon steel, nickel alloy, and lead alloy. In this case, while sufficiently utilizing the corrosion resistance and strength of titanium, it is possible to provide a cladding material having excellent thermal conductivity, electrical conductivity, light weight and workability.

The dissimilar metal plate is, for example, aluminum (Al) 99% by weight to 99.7% by weight; 0.1% to 1.0% by weight of silicon (Si); 0% to 0.05% by weight of magnesium (Mg); Zinc (Zn) 0% to 0.1% by weight; Manganese (Mn) 0 to 0.05% by weight; And the remainder of inevitable impurities; and may be an aluminum metal plate. In this case, while fully utilizing the ductility and strength of aluminum, it is possible to provide a cladding material having more excellent thermal conductivity, electrical conductivity, and light weight.

The dissimilar metal plate may have a thickness of 0.1 mm to 20 mm, specifically 0.1 mm to 10 mm, and more specifically 1 mm to 5 mm. Within the above range, the cladding material can further improve thermal conductivity, electrical conductivity, and light weight, while implementing excellent ductility and strength.

A plating layer is formed between the titanium metal plate and the dissimilar metal plate by an electroplating method. In this case, it may be performed following the etching process of removing the passivation film of the titanium metal plate, and the formation of the passivation film due to the oxidizing atmosphere (atmospheric contact) during the manufacturing process can be prevented by the plating layer formed on the surface.

Specifically, the plating layer may be a nickel plating layer. The nickel plating layer has excellent affinity for both the titanium metal plate and the dissimilar metal metal plate, and in particular, has excellent affinity for both titanium and aluminum, so that interfacial bonding strength can be further improved by high-temperature bonding.

The plating layer may have a thickness of 0.1 µm to 5 µm, specifically 1 µm to 3 µm, and more specifically 1 µm to 2 µm. Within the above range, the cladding material realizes excellent surface oxidation prevention ability and sufficient interfacial bonding strength, while reducing the amount of raw materials required for forming the plating layer, further lowering the production cost and further improving the efficiency in the manufacturing process.

The thickness ratio of the titanium metal plate and the dissimilar metal metal plate may be 1: 1.5 to 2.5. Within the above range, the interfacial bonding strength, strength, bonding strength, and drawing ratio of the cladding material of the titanium clad material can be realized to an excellent degree, the formation of intermetallic compounds at the interface is reduced, and embrittlement prevention ability can be realized.

1 is a schematic cross-sectional view of a cladding material according to an embodiment of the present invention. Referring to FIG. 1, the cladding material according to an embodiment of the present invention includes a titanium metal plate 10 as a base material, and a plating layer 20 formed by electroplating on the surface of the titanium metal plate 10 and titanium through the plating layer 20 are interposed. A dissimilar metal plate 30 bonded to one surface of the metal plate 10 may be included.

2 is a schematic cross-sectional view of a cladding material according to another embodiment of the present invention. Referring to FIG. 2, the cladding material of another embodiment of the present invention includes a titanium metal plate 10 as a base material, and a plating layer 20 formed by electroplating on the surface of the titanium metal plate 10 and titanium through the plating layer 20 are interposed. It may include dissimilar metal metal plates 31 and 32 bonded to both surfaces of the metal plate 10. At this time, the dissimilar metal metal plate 31 on one side and the dissimilar metal metal plate 32 on the other side may be of the same type or different types of metal.

Another embodiment of the present invention relates to a method of manufacturing the aforementioned cladding material. 3 is a schematic diagram of an exemplary method of manufacturing a cladding material of the present invention. Referring to Figure 3, the clad material manufacturing method of the present invention is a pre-treatment step (S1) of removing the oxide film of the titanium metal plate; Forming a plating layer by performing electroplating on the surface of the titanium metal plate from which the oxide film has been removed (S2); Heat-treating the titanium metal plate and the dissimilar metal plate on which the plating layer is formed at a temperature of 200°C to 400°C, respectively (S3); Laminating the heat-treated dissimilar metal plate on at least one surface of the titanium metal plate on which the plating layer is formed (S4), and then rolling the laminate at a reduction ratio of 20% to 30% (S5); And annealing heat treatment of the rolled laminate at 250° C. to 500° C. (S6). Includes.

Details of the titanium metal plate, the dissimilar metal plate, and the plating layer are the same as described above.

The pre-treatment step (S1) is to remove the passivation film formed on the surface of the raw material by etching the titanium metal plate. Specifically, the pretreatment step may be to etching the titanium metal plate with a mixture of at least one of NaF and NaHF _{2 and at} least one of hydrochloric acid, nitric acid and acetic acid. In this case, while omitting the use of a high-risk solvent such as hydrofluoric acid as an etching solution, loss of the thickness of the titanium metal plate due to etching can be reduced, and surface treatment suitable for electroplating for forming a plating layer can be performed.

Specifically, the mixture is at least one of NaF and NaHF ₂ ; and at least one of hydrochloric acid, nitric acid, and acetic acid; from 1:1 to 1:2, more specifically 1:1.0 to 1:1.5, even more specifically It may be included in a molar ratio of 1:0.85 to 1:0.58. In this case, while increasing the etching efficiency, it is possible to further reduce the loss of the thickness of the titanium metal plate due to etching, and perform surface treatment suitable for electroplating for forming a plating layer.

In addition, in the pretreatment step, an anodizing treatment may be additionally performed to form an anodic titanium hydroxide film on the titanium surface. In this case, the effect of suppressing additional oxidation may be further improved.

More specifically, the mixed solution may further contain water additionally to control the concentration. The mixed solution and water may be mixed in a weight ratio of 1:0.1 to 1:1. In this case, while increasing the etching efficiency, it is possible to further reduce the loss of the thickness of the titanium metal plate due to etching.

In the step of forming the plating layer, plating is performed on the surface of the titanium metal plate from which the oxide film has been removed. Specifically, the plating may be electroplating, electroless plating, sputtering, or the like. The electroplating may be performed continuously following the pretreatment step. For example, the electroplating may be to perform plating at a current density of 1 ASD (A/dm ² ) to 10 ASD (A/dm ² ) after successively immersing a pre-treated titanium metal plate in a metal electrolyte. have. Within the above range, a plating layer capable of sufficiently realizing interfacial bonding strength while reducing the amount of electric energy required for forming the plating layer may be formed, thereby further lowering the production cost and further improving the efficiency in the manufacturing process.

The metal electrolyte is a solution containing a metal salt, and may include, for example, at least one of a nickel sulfate solution and a nickel sulfamate solution to form a nickel plating layer. Within the above range, by reducing the amount of the nickel raw material required to form the plating layer, it is possible to further lower the production cost and further improve the efficiency in the manufacturing process.

The metal salt content of the metal electrolyte may be, for example, 50 g/L to 500 g/L. Within the above range, by reducing the amount of raw materials required for forming the plating layer, the production cost can be further lowered and the efficiency in the manufacturing process can be further improved.

In the heat treatment, the titanium metal plate on which the plating layer is formed and the dissimilar metal metal plate are separately heat treated at a temperature of 200°C to 400°C. This makes it possible to make the titanium metal plate and the dissimilar metal plate into a state suitable for bonding.

When the heat treatment temperature of the titanium metal plate is less than 200° C., it is difficult to implement an interfacial bonding strength sufficient to be used as a cladding material, and it is difficult to prevent the formation of intermetallic compounds. Conversely, when the heat treatment temperature of the titanium metal plate is higher than 400° C., the plating layer formed on the surface may be oxidized to reduce bonding strength. The heat treatment temperature of the titanium metal plate may be specifically 250°C to 400°C, more specifically 350°C to 400°C. In this case, the cladding material may include a titanium metal plate and a plating layer; And the bonding strength of the dissimilar metal plate may be further improved.

When the heat treatment temperature of the dissimilar metal sheet is less than 200° C., it is difficult to implement an interfacial bonding strength sufficient to be used as a cladding material, and it is difficult to prevent the formation of intermetallic compounds. Conversely, when the heat treatment temperature of the dissimilar metal sheet exceeds 400°C, shape defects may occur due to the rolling tension of the dissimilar metal sheet, and the dissimilar metal sheet may be melted or the intermetallic compound may be excessively formed, resulting in a decrease in bonding strength. . The heat treatment temperature of the dissimilar metal plate may be specifically 240°C to 400°C, more specifically 320°C to 400°C. In this case, the cladding material may include a titanium metal plate and a plating layer; And the bonding strength of the dissimilar metal plate may be further improved.

In the rolling step, the heat-treated dissimilar metal plate is laminated on at least one side of the heat-treated titanium metal plate after the plating layer is formed, and then the laminate is hot-rolled at a reduction ratio of 20% to 30% to be joined. When the reduction ratio is less than 20%, it is difficult to implement an interfacial bonding strength sufficient to be used as a cladding material. Conversely, when the reduction ratio is more than 30%, the amount of work hardening of the clad material is excessively high, so that the bonding strength may decrease. The reduction ratio may be specifically, 20% to 27%, more specifically 24% to 26%. Within the above range, the interfacial bonding strength and the work hardening amount can be implemented in a balanced manner, and the interfacial bonding strength of the cladding material may be further improved.

In the step of annealing heat treatment, the rolled laminate is subjected to annealing heat treatment at a temperature of 250°C to 500°C. When the annealing heat treatment temperature is less than 250° C., it is difficult for the cladding material to achieve improved strength compared to each of the titanium metal plates or dissimilar metal plates. Conversely, when the heat treatment temperature of the dissimilar metal sheet exceeds 500°C, there is a possibility of shape deformation, and production efficiency may decrease due to maintaining a high-temperature manufacturing process. The annealing heat treatment temperature may be specifically, 400°C to 500°C, more specifically 450°C to 500°C. Within the above range, the strength of the cladding material, the interfacial bonding force, and the drawing ratio can be improved to a more excellent degree while implementing the interfacial bonding force and the work hardening amount in a balanced manner.

FIG. 4 is a schematic diagram of a facility used for manufacturing a cladding material according to an embodiment of the present invention. Referring to FIG. 4, a titanium metal plate coil is uncoiled in a first pay off reel, and then a titanium metal plate uncoiled in a plate shape is a first induction heater through a roll feeder After moving to the (1st induction heater), the heat treatment step can be performed. Next, the dissimilar metal plate coil is uncoiled on a 2nd pay off reel, laminated on a heated titanium metal plate and a pinch roll, and a second induction heater After moving to ), the heat treatment step can be performed. Alternatively, after uncoiling the dissimilar metal plate coil on the 2nd pay off reel, moving to the 2nd induction heater and performing the heat treatment step, the heated titanium metal plate And may be stacked on a pinch roll. The laminated and heated clad material as described above may be transferred to a tension reel through a rolling step in a mill house and then used in the form of a coil.

The cladding material manufacturing method of the present invention may be performed in a continuous process as exemplarily indicated in FIG. 4. Through this, while omitting the explosion process or the vacuum process, it is possible to continuously perform with a manufacturing process other than bonding, and the manufacturing process is simplified, thereby remarkably reducing product unit cost and production cost.

Example

Hereinafter, the present invention will be described in detail through examples and comparative examples. However, these are only provided to explain the present invention in detail, and the scope of the present invention is not limited thereto.

Example 1

After immersing a grade 1 titanium metal plate of 0.5mmT x 150mmW x Coil in an etching solution, the surface was etched at room temperature for 20 seconds to remove the passivation film on the surface of the titanium metal plate. At this time, the etching solution was prepared by mixing NaF (NaHF ₂ ) and HNO ₃ in a molar ratio of 1:1.5.

The etched titanium metal plate was rinsed with distilled water and then immersed in an anodizing solution containing NaF (NaHF ₂ ) and CH ₃ COOH in a molar ratio of 1:0.58, and anodized with a current density of 2ASD and an electrolysis time of 30 seconds. A titanium hydroxide film was formed on the surface of titanium by connecting the deposited metal plate to the anode and the carbon plate to the cathode, and the anodized titanium metal plate was rinsed with distilled water.

The electroplating bath was equipped with a nickel metal salt solution (nickel sulfamate (Ni(NH ₂ SO ₃ ) ₂ ·4H ₂ O) 500 g/L, nickel chloride (NiCl ₂ ) 40 g/L, boric acid 40 g/L) as a plating solution, Electric nickel plating was performed on the pretreated titanium metal plate in the electroplating bath at a current density of 5 ASD (A/dm ² ) to form a nickel plating layer having a thickness of 1 μm.

The titanium metal plate on which the nickel plated layer was formed was heated at 350° C., and at the same time, an aluminum metal plate of 1.0 mmT x 150 mmW x coil Al 1050 steel type was heated at 240° C. to heat treatment.

After manufacturing a laminate by superposing an aluminum metal plate on one surface of each of the heat-treated titanium metal plates, it was hot-rolled and bonded by an induction heating method while controlling the reduction ratio to 25% with a work roll force (KN).

The lowered laminate was subjected to annealing heat treatment at 400° C. for 30 minutes, and then cooled at room temperature to prepare a cladding material.

Examples 2 to 19 and Comparative Examples 1 to 12

A cladding material was manufactured in the same manner as in Example 1, except that the manufacturing process conditions were changed as described in Tables 1 to 5 below.

Titanium metal plate Dissimilar metal plate Clad material Thickness(mm) Plating layer thickness (㎛) Heat treatment temperature (℃) Metal species Thickness(mm) Heat treatment temperature (℃) Reduction rate (%) Annealing heat treatment temperature (℃) Example 1 0.5 One 350 Ni One 240 25 400 Example 2 0.5 One 350 Ni One 320 25 400 Example 3 0.5 One 350 Ni One 400 25 400 Comparative Example 1 0.5 One 350 Ni One 21 25 400 Comparative Example 2 0.5 One 350 Ni One 185 25 400

Titanium metal plate Dissimilar metal plate Clad material Thickness(mm) Plating layer thickness (㎛) Heat treatment temperature (℃) Metal species Thickness(mm) Heat treatment temperature (℃) Reduction rate (%) Annealing heat treatment temperature (℃) Example 4 0.5 One 200 Ni One 320 25 400 Example 5 0.5 One 300 Ni One 320 25 400 Example 6 0.5 One 400 Ni One 320 25 400 Comparative Example 3 0.5 One 21 Ni One 320 25 400 Comparative Example 4 0.5 One 100 Ni One 320 25 400 Comparative Example 5 0.5 One 500 Ni One 320 25 400

Titanium metal plate Dissimilar metal plate Clad material Thickness(mm) Plating layer thickness (㎛) Heat treatment temperature (℃) Metal species Thickness(mm) Heat treatment temperature (℃) Reduction rate (%) Annealing heat treatment temperature (℃) Example 7 0.5 One 350 Ni One 320 20 400 Example 8 0.5 One 350 Ni One 320 24.6 400 Example 9 0.5 One 350 Ni One 320 25.3 400 Example 10 0.5 One 350 Ni One 320 27.3 400 Example 11 0.5 One 350 Ni One 320 25 400 Comparative Example 6 0.5 One 350 Ni One 320 13.3 400 Comparative Example 7 0.5 One 350 Ni One 320 14.9 400 Comparative Example 8 0.5 One 350 Ni One 320 15.3 400 Comparative Example 9 0.5 One 350 Ni One 320 16.6 400 Comparative Example 10 0.5 One 350 Ni One 320 16 400 Comparative Example 11 0.5 One 350 Ni One 320 19.3 400

Titanium metal plate Dissimilar metal plate Clad material Thickness(mm) Plating layer thickness (㎛) Heat treatment temperature (℃) Metal species Thickness(mm) Heat treatment temperature (℃) Reduction rate (%) Annealing heat treatment temperature (℃) Example 12 0.5 0.15 350 Ni One 320 25 400 Example 13 0.5 3 350 Ni One 320 25 400 Comparative Example 12 0.5 0 350 Ni One 320 25 400

Titanium metal plate Dissimilar metal plate Clad material Thickness(mm) Plating layer thickness (㎛) Heat treatment temperature (℃) Metal species Thickness(mm) Heat treatment temperature (℃) Reduction rate (%) Annealing heat treatment temperature (℃) Example 14 0.5 One 350 Ni One 320 25 250 Example 15 0.5 One 350 Ni One 320 25 300 Example 16 0.5 One 350 Ni One 320 25 350 Example 17 0.5 One 350 Ni One 320 25 400 Example 18 0.5 One 350 Ni One 320 25 450 Example 19 0.5 One 350 Ni One 320 25 500

<Method of evaluating physical properties>

(1) Interfacial bonding strength (unit: kgf/10mm): After collecting specimens with a size of 10 mm x 50 mm in length from the clad material prepared in the above-described Examples and Comparative Examples, T-peel off measurement method (ASTM D1876- 01), a peel off test was performed with a measuring device (hardness tester, KSU-2M) to measure the peel strength (interface bonding). The results are shown in Tables 6 to 10 below.

(2) Evaluation of plating property: After taking a specimen of 10 mm wide by 10 mm long from the cladding material prepared in Example 1, the appearance of the titanium metal plate before the plating layer was formed and the plate material after the nickel plating layer was formed. It was taken as an image, and the results are shown in FIG. 5. The plate materials before and after the plating were observed with the naked eye. In addition, the results according to the evaluation criteria are shown in Tables 6 to 10 below.

As a result of visual observation, plating peeling occurred, and if passivation occurred, the plating property was evaluated as defective and marked with "X". If passivation did not occur, but the adhesion outside the plating edge (high current) is good, the plating property is evaluated as normal. And marked as "○", and if passivation does not occur and adhesion of all parts including the plating edge is excellent, the plating property is evaluated as excellent and marked as "◎" The results are shown in Table 2 below.

(3) Component analysis: A specimen having a size of 10 mm x 10 mm in length was taken from the clad material prepared in Example 1 described above, and a cross section was photographed at X2000 magnification using a SEM-EDS SCANNING device, and the results are shown in FIG. 6 Shown in. The sheet materials before (A) and after (B) the rolling were analyzed for formation of intermetallic compounds using EDS, and their thickness was measured. The results are shown in Tables 6 to 10 below.

(4) Cupping test: A specimen having a size of 140 mm X 200 mm X 1.24 mmT was taken from the clad material prepared in the above-described Examples and Comparative Examples, followed by blanking under the following conditions, followed by cupping. The results are shown in FIGS. 7 to 9 below. In addition, the results according to the evaluation criteria are shown in Tables 6 to 10 below.

-Blanking: Φ85-3EA, Φ90-2EA, Φ95-2EA

-Cupping: Punch = Φ50 & R8 / Die = Φ53.88 & R6

BHF = 30 kN, Lub. = Uji, 90 mm.min (1.5mm/s)

-Molding height:

Φ85 = full flange drawing, 26mm height & Max.DrawingF.= 23.8kN

Φ90 = full flange drawing, 30 mm high & Max.DrawingF.= 26.1kN

Φ95 = 30 mm high drawing, Max.DrawingF.= 32.1kN

As a result of the cupping evaluation, when fracture of the joint portion occurs or a crack occurs at the processing edge, the cupping property is evaluated as defective and marked with “X”. No break or crack occurs, but when the cupping shape is poor, the cupping property is normal. It was evaluated and marked as "△", and if no fracture or cracking occurred and the cupping shape was excellent, the cupping property was evaluated as excellent and marked as "○"

(5) Drawing ratio: The drawing ratio was calculated according to Equation 1 below from the cladding materials prepared in the above-described Examples and Comparative Examples, and is shown in Table 2 below.

<Equation 1>

Drawing ratio = (A / B)

In Equation 1, A is the value of the drawing blank diameter (mm) of the cladding material, and B is the value of the drawing height (mm). The A value was 95 mm.

(One)
Interface bonding strength (kgf/mm) (2)
Plating evaluation (3) component analysis
(㎛) (4)
Cupping test (5) drawing cost Example 1 10 ○ 0 ○ 1.7 Example 2 35 ◎ 0 ◎ 1.9 Example 3 38 ◎ 0 ◎ 1.9 Comparative Example 1 2 × 0 × × Comparative Example 2 5 × 0 × ×

As can be seen from Table 6, Examples 1 to 3 of the present invention in which the heat treatment temperature of the dissimilar metal metal plate is 200°C to 400°C are applied to Comparative Examples 1 and 2 in which the heat treatment temperature of the dissimilar metal metal plate is outside the above range. Compared to that, it realized remarkably excellent interfacial bonding strength, plating properties, and cupping moldability. In addition, in Comparative Examples 1 and 2, shape defects occurred, and the evaluation of the drawing ratio was impossible.

(One)
Interface bonding strength (kgf/mm) (2)
Plating evaluation (3) component analysis
(㎛) (4)
Cupping test (5) drawing cost Example 4 28 ◎ 0 ◎ 1.9 Example 5 30 ◎ 0 ◎ 1.9 Example 6 36 ◎ 0 ◎ 1.9 Comparative Example 3 20 ◎ 0 ○ 1.7 Comparative Example 4 25 ◎ 0 ○ 1.8 Comparative Example 5 26 ◎ 0 ◎ 1.9

As can be seen from Table 7, Examples 4 to 6 of the present invention in which the heat treatment temperature of the titanium metal plate is 200° C. to 400° C. are further compared to Comparative Examples 3 to 6 in which the heat treatment temperature of the titanium metal plate is out of the above range. Implemented improved cupping moldability.

(One)
Interface bonding strength (kgf/mm) (2)
Plating evaluation (3) component analysis
(㎛) (4)
Cupping test (5) drawing cost Example 7 27 ◎ 0 ◎ 1.8 Example 8 30 ◎ 0 ◎ 1.9 Example 9 35 ◎ 0 ◎ 1.9 Example 10 31 ◎ 0 ◎ 1.7 Example 11 35 ◎ 0 ◎ 1.9 Comparative Example 6 5 × 0 × × Comparative Example 7 10 ○ 0 ○ 1.7 Comparative Example 8 13 ○ 0 ○ 1.7 Comparative Example 9 15 ○ 0 ○ 1.7 Comparative Example 10 14 ○ 0 ○ 1.7 Comparative Example 11 25 ◎ 0 ○ 1.8

As can be seen from Table 8, Examples 7 to 11 of the present invention having a reduction ratio of 20% to 30% significantly improved interfacial bonding strength and plating compared to Comparative Examples 6 to 11 in which the reduction ratio was out of the above range. And cupping moldability were implemented.

(One)
Interface bonding strength (kgf/mm) (2)
Plating evaluation (3) component analysis
(㎛) (4)
Cupping test (5) drawing cost Example 12 20 ○ 0 ○ 1.7 Example 13 38 ◎ 0 ◎ 1.9 Comparative Example 12 2 × 0 ○ ×

As can be seen from Table 9, Examples 12 to 13 of the present invention in which a nickel plated layer was interposed realized significantly improved interfacial bonding strength, plating property, and cupping moldability compared to Comparative Example 12 in which the plated layer was not formed. . In addition, in Comparative Example 12, a shape defect occurred, and the evaluation of the drawing ratio was impossible.

(One)
Interface bonding strength (kgf/mm) (2)
Plating evaluation (3) component analysis
(㎛) (4)
Cupping test (5) drawing cost Example 14 25 ◎ 0 ◎ 1.8 Example 15 27 ◎ 0 ◎ 1.8 Example 16 30 ◎ 0 ◎ 1.9 Example 17 35 ◎ 0 ◎ 1.9 Example 18 38 or more ◎ 0 ◎ 1.9 Example 19 38 or more ◎ 0.02 ○ 1.9

As can be seen from the results of Tables 2 to 10, the cladding material manufactured through the manufacturing method of Examples 1 to 19 of the present invention omits the explosion process or the vacuum process, while continuing with manufacturing processes other than bonding. It has excellent interfacial bonding strength, and effectively prevents the formation of a passivation film that occurs during the manufacturing process after etching, and can be manufactured without oxidation in a high-temperature oxidizing atmosphere, and has excellent strength, bonding strength and drawing ratio of materials The formation of intermetallic compounds at the interface is reduced, and a titanium cladding material having anti-embrittlement ability and a method for producing the same are provided.

10: titanium metal plate
20: plating layer
30, 31, 32: dissimilar metal plate

Claims (10)

Titanium metal plate;
A dissimilar metal plate bonded to at least one surface of the titanium metal plate; And
A plating layer interposed between the titanium metal plate and the dissimilar metal plate;
Cladding material containing.
The method of claim 1,
The plating layer is a nickel plating layer clad material.
The method of claim 1,
The dissimilar metal metal plate is a clad material which is a metal plate containing at least one of aluminum, stainless steel, copper, high carbon steel, nickel alloy, and lead alloy.
The method of claim 1,
The thickness ratio of the titanium metal plate and the dissimilar metal metal plate is 1: 1.5 to 2.5 clad material.
The method of claim 1,
The cladding layer is formed to a thickness of 0.1 ㎛ to 5 ㎛.
A pretreatment step of removing the oxide film of the titanium metal plate;
Forming a plating layer by performing electroplating on the surface of the titanium metal plate from which the oxide film has been removed;
Heat-treating the titanium metal plate and the dissimilar metal plate on which the plating layer is formed at a temperature of 200°C to 400°C, respectively;
Laminating the heat-treated dissimilar metal plate on at least one surface of the titanium metal plate on which the plating layer is formed, and then rolling the laminate at a reduction ratio of 20% to 30%; And
Annealing heat treatment at a temperature of 250°C to 500°C on the rolled laminate; Clad material manufacturing method comprising a.
The method of claim 6,
The pretreatment step is a titanium metal plate,
At least one of NaF and NaHF ₂ ; and
Treatment with a mixture of at least one of hydrochloric acid, nitric acid and acetic acid;
Clad material manufacturing method.
The method of claim 6,
The dissimilar metal metal plate is a metal plate comprising at least one of aluminum, stainless steel, copper, high carbon steel, nickel alloy, and lead alloy.
The method of claim 6,
In the step of forming the plating layer, the plating layer is formed to a thickness of 0.1 μm to 5 μm.
The method of claim 6,
In the annealing heat treatment step, the annealing heat treatment temperature is 400 ℃ to 500 ℃ clad material manufacturing method.

Images