US20070272681A1

US20070272681A1 - Clad Material, Method for Manufacturing Said Clad Material, and Apparatus for Manufacturing Said Clad Material

Info

Publication number: US20070272681A1
Application number: US10/589,193
Authority: US
Inventors: Tomoaki Yamanoi; Kazuhiko Minami
Original assignee: Showa Denko KK
Current assignee: Resonac Holdings Corp
Priority date: 2004-02-12
Filing date: 2005-02-10
Publication date: 2007-11-29
Also published as: EP1713601A4; JP2005254329A; WO2005077569A1; EP1713601A1; CN1933928A

Abstract

A method for manufacturing a clad material in which a core material is cast and skin materials are pressure-bonded thereon aims to prevent deterioration of adhesiveness of the core material and the skin materials while keeping sufficient cooling rate of the core material, prevent thickness variation and/or breakage of the skin materials during the manufacturing process, and keep the surface property of the cooling rolls constant. The method for manufacturing a clad material (11) includes the steps of continuously supplying molten metal (M) into a gap between a pair of cooling rollers (2 a) (2 b) to cast a core material, and cladding skin materials (10 a) (10 b) on both surfaces of the core material with hot rolling by continuously supplying the skin materials on peripheral surfaces of the cooling rollers so that the skin materials prevent direct contact between the cooling rollers and the molten metal, wherein the skin materials are supplied so as to come into contact with the peripheral surfaces of the cooling rollers, and wherein a contact distance (L1) from a contact starting point (P1) where the skin material begins to come into contact with the cooling roller to a meeting point (P2) where the skin material begins to come into contact with the molten metal is set to 100 times or more of a thickness (t1) of the skin material.

Description

Priority is claimed to Japanese Patent Application No. 2004-35186 filed on Feb. 12, 2004, and U.S. Provisional Application No. 60/545,530 filed on Feb. 19, 2004, the disclosure of which are incorporated by reference in their entireties.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is an application filed under 35 U.S.C.§111(a) claiming the benefit pursuant to 35 U.S.C.§119(e)(1) of the filing date of U.S. Provisional Application No. 60/545,530 filed on Feb. 19, 2004, pursuant to 35 U.S.C.§111(b).

TECHNICAL FIELD

The present invention relates to a clad material with skin materials laminated on both sides of a core material for giving, for example, brazing performance and corrosion resistance, especially, a clad material excellent in high-temperature strength, a method for manufacturing such clad material, and an apparatus for manufacturing such clad material.

BACKGROUND ART

The following description sets forth the inventor's knowledge of related art and problems therein and should not be construed as an admission of knowledge in the prior art.
In recent years, in accordance with reduction in size and weight and improvement in performance of heat exchanges, the materials thereof are required to be thin in thickness and high in strength. Furthermore, for the purpose of decreasing environmental burden, a request of alternatives for chlorofluorocarbon has increased, and therefore a request of heat exchangers using CO₂as refrigerant has increased. Examples of such heat exchangers meeting the above demands include heat exchangers represented by radiators and heater cores, which use water as a principal component of refrigerant, heat exchangers represented by condensers and evaporators, which use fleon gas as refrigerant, and heat exchangers represented by gas coolers (evaporators), which use CO₂as refrigerant.
As a component for use in these heat exchangers, a clad material consisting of an aluminum alloy core and an aluminum alloy skin material which gives brazing performance and corrosion prevention performance to the surface of the core and having sufficient strength even after brazing has been used. In a generally employed method for manufacturing such clad material, a pre-heated ingot is hot-rolled and then the surface thereof is scraped to obtain a core material having a thickness of 250 mm to 400 mm. The core material and a skin material having a thickness of 10 to 100 mm are placed one on another and then temporarily fixed with each other. Thereafter, the temporarily fixed members are subjected to hot-rolling, cold-rolling and, if necessary, intermediate annealing.
As a material of the aforementioned aluminum alloy core material, there is an Al—Mn series alloy plate improved in high temperature strength by manufacturing under predetermined heat-treating conditions and rolling conditions. However, although these Al—Mn series alloy plates are excellent in characteristics as elementary substance, they can give simultaneously neither brazing performance nor corrosion prevention performance (Japanese Unexamined Laid-open Patent Publication No. 2000-104149 and Japanese Unexamined Laid-open Patent Publication No. 2002-241910).
Moreover, as for the method for manufacturing a clad material, in place of the aforementioned hot-rolling method, various methods utilizing continuous casting of core materials have been proposed (Japanese Unexamined Laid-open Patent Publication No. H11-226699, Japanese Laid-open Patent Publication No. H8-509265 and Japanese Laid-open Patent Publication No. 2002-248599).
Japanese Unexamined Laid-open Patent Publication No. H11-226699 discloses a method for continuously manufacturing a clad material in which a skin material is pressure-bonded to a core material which is being sent out from a cast rolling mill with pressure-bonding rolls disposed at the vicinity of the outlet side of the rolling mill. Also disclosed in FIGS. 11 e and 11 f of Japanese Laid-open Patent Publication No. H8-509265 is a method for continuously casting a core material and cladding of the core material and a skin material with pressure-bonding rolls disposed at the outlet side of the cooling rollers of the cast rolling mill.
On the other hand, disclosed in FIGS. 11 a, 11 b and 11 c of Japanese Laid-open Patent Publication No. H8-509265 is a method for manufacturing a clad material in which casting of a core material and pressure-bonding of the core material and the skin material are simultaneously performed by supplying the skin material at the inlet side of molten alloy with cooling rollers of the cast rolling apparatus. Also disclosed in Japanese Laid-open Patent Publication No. 2002-248599 is a method for supplying a skin material at the inlet side of cooling rollers for casting a core material when manufacturing a clad material in which the width of the skin material is wider than that of the core material and the skin material is embedded in the core material.
However, there were the following problems in the manufacturing method of the aforementioned clad material.
That is, according to the method in which pressure-bonding of the skin material to the core material is performed after the casting of the core material, since it is necessary to arrange a cast rolling mill and a pressure-bonding roll, the equipment becomes complicated in structure, and the production rate is restricted by the continuous casting rate of the core material. Furthermore, deterioration of adhesiveness of the skin material due to a segregation layer containing oxide formed on the surface at the time of continuous cast rolling and deterioration of corrosion characteristics at the interface cannot be suppressed.
On the other hand, according to the method for simultaneously performing the casting of the core material and the pressure-bonding of the skin material to the core material, since the position where the skin material comes into contact with the molten metal (core material) at the inlet side of the cooling rollers becomes unstable, a part of the skin material may melt, or even may be broken. Furthermore, according to Japanese Laid-open Patent Publication No. 2002-248599, since the width of the core material is larger than that of the skin material and therefore the molten metal partially comes into contact with the cooling rollers, the roll surface property changes, resulting in difficulty in controlling the roll surface property for a long time.
The description herein of advantages and disadvantages of various features, embodiments, methods, and apparatus disclosed in other publications is in no way intended to limit the present invention. Indeed, certain features of the invention may be capable of overcoming certain disadvantages, while still retaining some or all of the features, embodiments, methods, and apparatus disclosed therein.
Other objects and advantages of the present invention will be apparent from the following preferred embodiments.

DISCLOSURE OF INVENTION

The preferred embodiments of the present invention have been developed in view of the above-mentioned and/or other problems in the related art. The preferred embodiments of the present invention can significantly improve upon existing methods and/or apparatuses.
The present invention was made in view of the aforementioned problems, and aims to provide a method for manufacturing a clad material capable of keeping the surface property of cooling rollers constant while keeping high cooling rate of a core material, restraining deterioration of adhesiveness of a skin layer due to contamination of non-metallic inclusion such as an oxide film formed at the interface of the skin material and the core material, and restraining occurrence of thickness variation of the skin material after the cladding and/or breakage of the skin material during the manufacturing process. Furthermore, the present invention also aims to provide a clad material manufactured by the aforementioned method and an apparatus for manufacturing a clad material for executing the aforementioned method.
The method for manufacturing a clad material according to the present invention has the following structures as recited in Items (1) to (11).
(1) A method for manufacturing a clad material, comprising the steps of:
continuously supplying molten metal into a gap between a pair of cooling rollers to cast a core material; and
cladding skin materials on both surfaces of the core material with hot rolling by continuously supplying the skin materials on peripheral surfaces of the cooling rollers so that the skin materials prevent direct contact between the cooling rollers and the molten metal,
wherein the skin materials are supplied so as to come into contact with the peripheral surfaces of the cooling rollers, and
wherein a contact distance (L1) from a contact starting point (P1) where the skin material begins to come into contact with the cooling roller to a meeting point (P2) where the skin material begins to come into contact with the molten metal is set to 100 times or more of a thickness (t1) of the skin material.
(2) The method for manufacturing a clad material as recited in the aforementioned Item 1, wherein the core material and the skin material are made of aluminum or its alloy.
(3) The method for manufacturing a clad material as recited in the aforementioned Item 1, wherein the thickness (t1) of the skin material is 20 to 400 μm.
(4) The method for manufacturing a clad material as recited in the aforementioned Item 2, wherein at least one of the skin materials is made of Al—Si series alloy.
(5) The method for manufacturing a clad material as recited in the aforementioned Item 4, wherein the Al—Si series alloy consists essentially of
Si: 5 to 15 mass %,
Fe: 0.05 to 0.6 mass %,
Cu: 0.01 to 0.6 mass %,
Mn: 0.01 to 0.8 mass %,
Mg: 0.01 to 0.2 mass %,
Ti: 0.01 to 0.2 mass %, and
the balance being Al and inevitable impurities.
(6) The method for manufacturing a clad material as recited in the aforementioned Item 2, wherein at least one of the skin materials is made of Al—Zn series alloy.
(7) The method for manufacturing a clad material as recited in the aforementioned Item 6, wherein the Al—Zn series alloy consists essentially of
Si: 0.05 to 0.6 mass %,
Fe: 0.05 to 0.6 mass %,
Cu: 0.01 to 0.6 mass %,
Mn: 0.01 to 0.8 mass %,
Mg: 0.01 to 0.2 mass %,
Ti: 0.01 to 0.2 mass %,
Zn: 0.35 to 8.5 mass %, and
the balance being Al and inevitable impurities.
(8) The method for manufacturing a clad material as recited in the aforementioned Item 1, wherein a thickness (t2) of the skin material after hot roll cladding is 0.5 to 8 mm.
(9) The method for manufacturing a clad material as recited in the aforementioned Item 2, wherein the molten metal to become the core material consists essentially of
Si: 0.05 to 1.5 mass %,
Fe: 0.05 to 2 mass %,
Cu: 0.05 to 0.8 mass %,
Mn: 0.15 to 2.8 mass %,
at least one of elements selected from the group consisting of Cr: 0.03 to 0.7 mass %, Mg: 0.01 to 0.2 mass %, Ti: 0.01 to 0.3 mass %, and Zn: 0.01 to 1.5 mass %, and
the balance being Al and inevitable impurities.
(10) The method for manufacturing a clad material as recited in the aforementioned Item 9, wherein the molten metal further includes at least one of elements selected from the group consisting of Zr: 0.15 to 1.5 mass %, V: 0.03 to 1.5 mass %, and Sc: 0.02 to 0.5 mass %.
(11) The method for manufacturing a clad material as recited in any one of the aforementioned Items 1 to 10, wherein cold rolling is performed after the hot roll cladding.
A clad material according to the present invention has the following structures as recited in Items (12) to (15).
(12) A clad material in which skin materials are clad on both surfaces of a core material, wherein the clad material is manufactured by the steps of continuously supplying molten metal into a gap between a pair of cooling rollers to cast a core material, and cladding skin materials on both surfaces of the core material with hot rolling by continuously supplying the skin materials on peripheral surfaces of the cooling rollers so that the skin materials prevent direct contact between the cooling rollers and the molten metal, wherein the skin materials are supplied so as to come into contact with the peripheral surfaces of the cooling rollers, and wherein a contact distance (L1) from a contact starting point (P1) where the skin material begins to come into contact with the cooling roller to a meeting point (P2) where the skin material begins to come into contact with the molten metal is set to 100 times or more of a thickness (t1) of the skin material.
(13) The clad material as recited in the aforementioned Item 12, wherein the clad material is cold rolled after the hot roll cladding.
(14) The clad material as recited in the aforementioned Item 12, wherein an average dendrite secondary arm spacing of the core material formed by the heat roll cladding is 0.1 to 10 μm.
(15) The clad material as recited in any one of the aforementioned Items 12 to 14, wherein the clad material is heat exchanger component material.
The apparatus for manufacturing a clad material according to the present invention has the following structures as recited in Item (16).
(16) An apparatus for manufacturing a clad material, comprising:
a pair of cooling rollers for continuously casting molten metal passing through a gap formed between the cooling rollers;
a molten metal supplying portion for supplying the molten metal to become a core material into the gap; and
a skin material supplying portion for supplying a skin material on a peripheral surface of the cooling roller and making the skin material come into contact with the peripheral surface of the cooling roller before the skin material joins the molten metal,
wherein the cooling rolls are rotated while continuously supplying the molten metal and the skin material to the cooling rolls to thereby continuously clad the skin materials to both surfaces of the core material.

EFFECTS OF THE INVENTION

According to the manufacturing method of the clad material of the invention as recited in the aforementioned Item (1), since the skin materials are joined to the molten metal in a state in which the skin material is cooled, the molten metal is solidified quickly by being cooled by the cooling rollers. Therefore, a core material having high hardness can be cast and the skin materials can be pressure-bonded to both surfaces of the core material. Since the skin material is cooled in advance, melting and/or fusing of the skin material due to the heat of the molten metal M can be prevented, and a clad material can be manufactured efficiently without reducing the cooling rate of the core material. Moreover, since the aforementioned skin materials are pressure-bonded during the solidification process of the core material, high adhesion can be attained. Furthermore, since the cooling rollers and the molten metal are intercepted by the skin material, the alteration and deterioration of the roll surface property due to adhesion of the molten metal can be prevented.
According to the invention as recited in the aforementioned Item (2), the aforementioned clad material which consists of aluminum or its alloy can be manufactured.
According to the invention as recited in the aforementioned Item (3), tension control of the skin material can be performed smoothly, and sufficient cooling rate of the core material can be secured.
According to the invention as recited in the aforementioned Item (4), an aluminum brazing clad material with brazing material clad on the surface can be manufactured.
According to the invention as recited in the aforementioned Item (5), the aluminum brazing clad material excellent in especially brazing performance can be manufactured.
According to the invention as recited in the aforementioned Item (6), the aluminum brazing clad material excellent in corrosion resistance in which a sacrificial corrosion layer is formed on the surface can be manufactured.
According to the invention as recited in the aforementioned Item (7), the aluminum brazing clad material excellent in especially corrosion resistance can be manufactured.
According to the invention as recited in the aforementioned Item (8), molten metal can be supplied stably and it is possible to secure the heat releasing capacity from the cooling rollers.
According to the invention as recited in the aforementioned Item (9), an aluminum brazing clad material excellent in strength even at high temperature and excellent in corrosion resistance can be manufactured.
According to the invention as recited in the aforementioned Item (10), the aluminum material excellent in especially high temperature strength can be manufactured.
According to the invention as recited in the aforementioned Item (11), the clad material having a prescribed thickness can be manufactured.
The clad material according to the invention as recited in the aforementioned Item (12) is excellent in adhesiveness property between the skin materials and the core material, or is a useful clad material to which various characteristics, such as brazing performance, corrosion resistance and strength, are further added. Furthermore, the clad material is excellent in workability.
According to the invention as recited in the aforementioned Item (13), a clad material having a prescribed thickness can be obtained.
According to the invention as recited in the aforementioned Item (14), a clad material especially excellent in strength can be obtained.
According to the invention as recited in the aforementioned Item (15), the clad material is useful as a heat exchanger structure component material.
According to the manufacturing apparatus of a clad material of the invention as recited in the aforementioned Item (16), the manufacturing method of the present invention is executed and a clad material can be manufactured efficiently.
The above and/or other aspects, features and/or advantages of various embodiments will be further appreciated in view of the following description in conjunction with the accompanying figures. Various embodiments can include and/or exclude different aspects, features and/or advantages where applicable. In addition, various embodiments can combine one or more aspect or feature of other embodiments where applicable. The descriptions of aspects, features and/or advantages of particular embodiments should not be construed as limiting other embodiments or the claims.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view showing an apparatus structure for executing a method for manufacturing a clad material according to the present invention.
FIG. 2 is a perspective view showing a brazed article used in a brazing test.

BEST MODE FOR CARRYING OUT THE INVENTION

In the following paragraphs, some preferred embodiments of the invention will be described by way of example and not limitation. It should be understood based on this disclosure that various other modifications can be made by those in the art based on these illustrated embodiments.
A method for manufacturing a clad material according to a preferable embodiment of the present invention will be described in detail with reference to the clad material manufacturing apparatus 1 shown in FIG. 1.
In FIG. 1, the reference numeral 2 a and 2 b denote a pair of cooling rollers disposed at a certain distance, the reference numeral 3 denotes a nozzle which injects molten metal M supplied from a molten-metal preparation portion, such as a melting furnace and a tundish (not shown), into the gap between the aforementioned cooling rollers 2 a and 2 b. The aforementioned nozzle 3 sets the meeting point P2 of the molten metal M and the skin material 10 a and 10 b by the opening width and the set position. The aforementioned nozzle 3 demonstrates effective roles for preventing melt breakage of the skin material and holding the clad ratio (skin material/core material/skin material) constant. The reference numeral 4 a (4 b) denotes a holding roll for holding down the skin material 10 a (10 b) continuously supplied by unwinding the skin material coil (not shown) toward the cooling roller 2 a (2 b). By adjusting the holding position of the holding roll 4 a (4 b), the contact starting point P1 where the skin material 10 a (10 b) begins to come into contact with the cooling roller 2 a (2 b) is set. The reference numeral 11 denotes a plate-shaped core material made of cast molten metal M, and the reference numeral 12 denotes a three-layered clad material in which the skin materials 10 a and 10 b are clad on both surfaces of the aforementioned core material 11.
In the manufacturing method of the clad material according to the present invention, when supplying the skin material 10 a (10 b) to the cooling roller 2 a (2 b), the skin material 10 a (10 b) is cooled by coming into contact with the peripheral surface of the cooling roller 2 a (2 b) before joining the molten metal M, and therefore the skin material 10 a (10 b) joins the molten metal M in a cooled state. For this reason, the molten metal M supplied to the gap between the cooling rollers 2 a and 2 b is quickly solidified by being cooled by the cooling roller 2 a (2 b) even via the skin material 10 a (10 b), and the skin material 10 a (10 b) is pressure-bonded and clad on both surfaces of the core material 11. Furthermore, since the skin material 10 a (10 b) is to be pressure-bonded to the core material 11 during the solidification process of the core material 11, contamination, such as an oxide film, to the interface between the skin material 10 a (10 b) and the core material 11 can be prevented, resulting in excellent adhesiveness of the skin material 10 a (10 b) to the core material 11. Since the aforementioned skin material 10 a (10 b) is cooled beforehand, the melting and fusing of the skin material due to the heat of the molten metal M can be prevented, and therefore the clad material 12 can be manufactured efficiently without reducing the cooling rate of the core material 11. Moreover, since the molten metal M and the cooling roller 2 a (2 b) are intercepted by the aforementioned skin material 10 a (10 b), alteration and/or deterioration of the roll surface property due to the adhesion of the molten metal M can be prevented.
The contact distance L1 of the skin material 10 a (10 b) along which the aforementioned skin material 10 a(10 b) is pre-cooled by the cooling roller (2 a) 2 b, namely, the distance from the contact starting point P1 where the skin material 10 a (10 b) comes into contact with the cooling roller 2 a (2 b) to the meeting point P2 where the skin material 10 a (10 b) comes into contact with the molten metal M, it is necessary to set such that the contact distance L1 is set to a length of 100 times or more of the thickness t1 of the skin material 10 a (10 b) in order to fully cool the skin material 10 a (10 b) and to acquire the aforementioned effects. More preferably, the contact distance L1 is set to a length of 200 times to 100,000 times of the thickness t1 of the skin material 10 a (10 b).
It is possible to attain the aforementioned manufacturing conditions by setting the contact distance L1 so that the ratio of the contact distance to the thickness of the skin material (L1/t1) falls within the aforementioned range. For example, by changing the diameter of the cooling rollers 2 a (2 b) and the contact starting point P1 where the skin material 10 a (10 b) begins to come into contact with the cooling roller 2 a (2 b) so as to meet the aforementioned range, the range of the roller with which the skin material 10 a (10 b) is in contact, namely, the contact distance L1, can be adjusted. In cases where the contact distance L1 is represented by a center angle as seen from the center of the cooling roller 2 a (2 b), it is preferable to adjust the range of the center angle so as to fall within the range of from 10 to 270°. If it falls within this range, it becomes easy to arrange the devices, and the skin material can be stably wound on the cooling roller 2 a(2 b). It is more preferable to adjust the range so as to fall within the range of from 150 to 180°.
It is preferable that the thickness t1 of the aforementioned skin material 10 a (10 b) is 20 to 400 μm. If it is less than 20 μm, it becomes difficult to control the tension of the unwinding roll, which in turn makes it difficult to perform continuation operation due to the possible breakage of the skin material. On the other hand, if it exceeds 400 μm, the heat capacity of the skin material 10 a (10 b) increases. Therefore, the heat releasing capacity of the cooling roller 2 a (2 b) becomes insufficient, resulting in insufficient cooling rate. The preferable thickness t1 of the skin material 10 a (10 b) is 20 to 200 μm. The thickness of the skin material 10 a (10 b) is not required to be the same in both sides, and the skin materials different in thickness can be employed. Accordingly, the contact distances L1 of both skin materials can also be different with each other.
The thickness t2 of the core material 11 after the hot cladding is preferably 0.5 to 8 mm. Since the present invention employs continuous casting using a pair of cooling rollers 2 a and 2 b, if the plate thickness t2 after the cladding is less than 0.5 mm, the roll gap is too narrow to stably supply molten metal M. On the other hand, if the thickness exceeds 8 mm, the heat releasing capacity through the cooling roller 2 a (2 b) becomes insufficient, which makes it difficult to secure sufficient cooling rate of the core material. The preferable thickness t2 of the core material 11 is 0.8 to 6 mm.
As will be understood from the above, it is possible to cast a core material 11 excellent in high-temperature strength and efficiently manufacture a three-layered structural clad material 12 with skin materials 10 a and 10 b clad on both surfaces of the core material 11.
As for the aforementioned cooling rollers, the number of revolutions of the cooling rollers, and the materials of the cooling rollers, it is possible to employ conventionally known ones, provided that cooling conditions of materials are sufficiently met under the aforementioned L1/t1 condition. For example, the diameter of the roller is preferably 100 to 1,000 mm since such a cooling roll can be easily manufactured or obtained and therefore the entire apparatus can be constituted at lower cost. Furthermore, the number of revolutions of the cooling roller is preferably 1 to 200 m/min., more preferably 5 to 150 m/min. in circumferential velocity. As the materials of the cooling rollers, aluminum or its alloy, copper or its alloy, and iron or its alloy can be exemplified.
In the aforementioned clad material 12, the materials of the core material 11 and the skin material 10 a and 10 b are metal, and aluminum and its alloy can be exemplified as such metal. The clad material made of aluminum or its alloy can be used as component material which constitutes, for example, fluid passages, tubes, heat releasing fins of heat exchangers.
As the core material and the skin material made of aluminum or its alloy, the following material can be recommended.
As for the skin material, it is preferable to use Al—Si series alloy which functions as brazing material and Al—Zn series alloy which gives corrosion resistance.
As the aforementioned Al—Si series alloy, it is preferable to use alloy consisting of Si: 5 to 15 mass %, Fe: 0.05 to 0.6 mass %, Cu: 0.01 to 0.6 mass %, Mn: 0.01 to 0.8 mass %, Mg: 0.01 to 0.2 mass %, Ti: 0.01 to 0.2 mass %, and the balance being Al and inevitable impurities.
The reasons of adding each element in the aforementioned Al—Si series alloy are as follows.
Si is an element which makes the alloy function as brazing material by lowering the melting point of the alloy. The preferable Si content is 6.5 to 11 mass %. Fe is an element to be added to improve the wettability of brazing material, and if the content is less than 0.05 mass %, the effects will become poor. To the contrary, if it exceeds 0.6 mass %, large and rough intermetallic compound will be generated, which gives adverse effects on corrosion resistance. The preferable Fe content is 0.1 to 0.5 mass %. Cu is an element to be added to control the electric potential of the skin material (Al—Si series alloy). For example, in cases where the clad material 12 is used as a brazing tube of a heat exchanger, the electric potential of the brazing material becomes unnecessarily less noble with respect to the tube. Therefore, Cu is added to restrain an occurrence of preferential corrosion of fillets. The preferable Cu content is 0.02 to 0.5 mass %. Mn is an element to be added to control the electric potential of the brazing material like Cu. If the content exceeds 0.8 mass %, the flowing characteristics of the brazing material may be inhibited. The preferable Mn content is 0.02 to 0.6 mass %. Mg is an element to be added to improve the strength. If it is less than 0.01 mass %, the effects become poor. To the contrary, it exceeds 0.2 mass %, the brazing performance will be inhibited remarkably. The preferable Mg content is 0.01 to 0.1 mass %. Ti is an element to be added to control the electric potential of the brazing material. The preferable Ti content is 0.01 to 0.1 mass %.
As the aforementioned Al—Zn series alloy, it is preferable to use an alloy consisting of Si: 0.05 to 0.6 mass %, Fe: 0.05 to 0.6 mass %, Cu: 0.01 to 0.6 mass %, Mn: 0.01 to 0.8 mass %, Mg: 0.01 to 0.2 mass %, Ti: 0.01 to 0.2 mass %, Zn: 0.35 to 8.5 mass %, and the balance being Al and inevitable impurities.
The reasons of adding each element in the aforementioned Al—Zn series alloy are as follows.
Zn is an element which is dissolved in Al to make the skin material function as a sacrificial corrosion layer of the core material. The preferable Zn content is 0.35 to 6 mass %. Si is an element to be added to improve the strength, and the preferable Si content is 0.1 to 0.5 mass %. Although Fe is an element to be added to improve the strength, if it exceeds 0.6 mass %, large and rough intermetallic compounds will be generated, which may cause a deterioration of corrosion resistance. The preferable Fe content is 0.1 to 0.5 mass %. Cu is an element to be added to control the electric potential of the skin material. The preferable Cu content is 0.02 to 0.3 mass %. Mn is an element to be added to control the electric potential of the skin material. The preferable Mn content is 0.02 to 0.6 mass %. Mg is an element to be added to improve the strength. If it is less than 0.01 mass %, the effects cannot be obtained. To the contrary, if it exceeds 0.2 mass %, the brazing performance may be remarkably inhibited. The preferable Mg content is 0.01 to 0.1 mass %. Ti is an element to be added to control the electric potential of the skin material. The preferable Ti content is 0.01 to 0.1 mass %.
The skin material having the aforementioned composition can be clad on at least one surface of the core material. A skin material to be clad on the other surface of the core material can be a skin material having a composition the same as or different from that of the aforementioned skin material.
On the other hand, as the core material 11, i.e., the molten metal M, it is preferable to use alloy consisting of at least one of elements selected from the group consisting of Si: 0.05 to 1.5 mass %, Fe: 0.05 to 2 mass %, Cu: 0.05 to 0.8 mass %, Mn: 0.15 to 2.8 mass %, at least one element selected from the group consisting of Cr: 0.03 to 0.7 mass %, Mg: 0.01 to 0.2 mass %, Ti: 0.01 to 0.3 mass % and Zn: 0.01 to 1.5 mass %, and the balance being Al and inevitable impurities. Furthermore, in the composition of the aforementioned molten metal M, it is preferable to further contain at least one element selected from the group consisting of Zr: 0.15 to 1.5 mass %, V: 0.03 to 1.5 mass %, and Sc: 0.02 to 0.5 mass %.
The reasons of adding each element in the composition of the aforementioned core material are as follows.
Si is an element to be added to improve the strength, and the preferable Si content is 0.5 to 1.2 mass %. Fe is an element to be added to improve the strength. If it exceeds 2 mass %, intermetallic compounds, such as an Al—Fe—Mn—Si series, will be generated, which may inhibit corrosion resistance. The preferable Fe content is 0.1 to 0.5 mass %. Cu is an element to be added to control the electric potential, cause the electric potential to be noble than the electric potential of the skin material by adding Cu, and perform corrosion prevention of the core material. The preferable Cu content is 0.05 to 0.6 mass %. Mn is an element to be added to improve the strength, especially to improve the strength at high temperature. The preferable Mn content is 0.5 to 2.5 mass %. Cr is an element to be added to improve the high temperature strength, and the preferable Cr content is 0.05 to 0.3 mass %. Mg is an element which is dissolved in Al to improve the high temperature strength, and the preferable Mg content is 0.05 to 0.2 mass %. Ti makes electric potential noble, and is an element to be added to change the corrosion from pitting corrosion to layer corrosion, and the preferable Ti content is 0.05 to 0.25 mass %. Zn is an element added to control the electric potential, and the preferable Zn content is 0.1 to 1 mass %.
Zr, V, and Sc which are added arbitrarily are elements to be added for the purpose of raising the recrystallizing temperature and raising the high temperature strength. The preferable Zr content is 0.15 to 0.8 mass %. The preferable V content is 0.1 to 1 mass %. The preferable Sc content is 0.04 to 0.5 mass %. It is sufficient that at least one of Zr, V, and Sc is included. However, two or all of three elements can be included.
The clad material manufactured from the aluminum or aluminum alloy mentioned above can be formed into a predetermined thickness by further subjecting it to cold rolling if necessary. Moreover, heat treating after the cladding or cold rolling can also be performed arbitrarily.
The clad material manufactured by the manufacturing method of the present invention is excellent in high-temperature strength due to the rapid solidification of the core material. Furthermore, since the breakage thereof at the time of machining seldom occurs, the clad material can be a clad material excellent in workability. Especially in the crystalline structure of the core material, the clad material whose average dendrite secondary arm spacing (DAS) is 0.1 to 10 μm has high-temperature strength. The more preferable average dendrite secondary arm spacing is 0.1 to 8 μm. Furthermore, the skin material to which brazing performance and corrosion prevention performance was given by the skin material having the prescribed components can be preferably used as a brazing material of heat exchanger components, such as a fluid passage, a tube and a heat releasing fin, to be used in high temperature environment. Especially, the skin material can be used as structural components of heat exchangers using CO₂refrigerant that especially excellent high temperature strength is required.
The manufacturing apparatus for clad material according to the present invention is not limited to the manufacturing apparatus 1 having the structure shown in FIG. 1, but can employ various structures having the same function.
The cooling roller in the manufacturing apparatus of the present invention corresponds to the cooling roller 2 a and 2 b of the manufacturing apparatus 1 of the illustrated embodiment. Similarly, the molten-metal supplying portion corresponds to a molten-metal preparation portion which is located outside the drawing and arranged in front of the nozzle 3. The skin material feeding portion corresponds to the aforementioned holding roll 4 a (4 b) and the tension roll for adjusting the tension of the skin material coil located outside the drawing or the tension of the skin member, etc.

EXAMPLES

It should be understood that the following examples do not limit the scope of the invention.
Using the apparatus 1 for manufacturing the clad material as shown in FIG. 1 and explained above, the three-layered clad material 12 of the present invention was manufactured.

In each following Examples 1 to 3, as the alloy constituting a core material and a skin material, the aluminum alloys having the chemical composition shown in Table 1 were used.

TABLE 1


Alloy	Chemical composition (mass %), the balance being Al and inevitable impurities

No.

Si

Fe

Cu

Mn

Mg

Cr

Ni

Zn

Ti

Zr

V

Sc

(a)	0.10	0.25	0.02	0.01	0.01	<0.01	<0.01	0.02	0.01	<0.01	<0.01	<0.01
(b)	0.08	0.20	0.02	0.01	0.01	<0.01	<0.01	0.04	0.01	0.18	<0.01	<0.01
(c)	0.25	0.50	0.12	0.02	0.01	0.01	<0.01	0.04	0.05	<0.01	<0.01	<0.01
(d)	0.25	0.40	0.15	1.05	0.01	0.01	<0.01	0.05	0.02	<0.01	<0.01	<0.01
(e)	0.25	0.40	0.15	0.95	0.01	0.20	<0.01	0.05	0.05	0.18	<0.01	<0.01
(f)	7.85	0.65	0.07	0.04	0.02	0.01	<0.01	0.10	0.02	<0.01	<0.01	<0.01
(g)	0.30	0.60	0.14	0.05	1.52	0.04	<0.01	0.15	0.05	<0.01	<0.01	<0.01
(h)	0.20	0.35	0.07	0.07	2.25	0.24	<0.01	0.08	0.05	<0.01	<0.01	<0.01
(i)	0.48	0.33	0.05	0.04	0.55	0.03	<0.01	0.04	0.03	<0.01	<0.01	<0.01
(j)	0.20	0.42	0.05	0.04	0.03	<0.01	<0.01	1.15	0.10	<0.01	<0.01	<0.01
(k)	0.30	0.45	1.65	0.25	2.55	0.22	<0.01	5.55	0.10	0.18	<0.01	<0.01
(l)	0.25	0.40	0.18	1.05	0.01	0.01	<0.01	0.05	0.02	<0.01	<0.01	<0.01
(m)	4.55	0.55	0.06	0.04	0.02	0.01	<0.01	2.20	0.02	<0.01	<0.01	<0.01
(n)	8.85	0.65	0.07	0.04	0.02	0.01	<0.01	2.20	0.02	<0.01	<0.01	<0.01
(o)	15.80	0.64	0.07	0.04	0.02	0.01	<0.01	2.20	0.02	<0.01	<0.01	<0.01
(p)	0.20	0.42	0.05	0.04	0.03	<0.01	<0.01	0.15	0.10	<0.01	<0.01	<0.01
(q)	0.20	0.42	0.05	0.04	0.03	<0.01	<0.01	2.55	0.10	<0.01	<0.01	<0.01
(r)	0.20	0.42	0.05	0.04	0.03	<0.01	<0.01	10.50	0.10	<0.01	<0.01	<0.01
(s)	0.30	0.38	0.05	1.05	0.01	0.01	<0.01	1.50	0.02	<0.01	<0.01	<0.01
(t)	8.50	0.45	0.10	0.04	0.02	0.01	<0.01	1.50	0.04	<0.01	<0.01	<0.01
(u)	0.60	0.40	0.35	0.05	0.10	0.05	<0.01	0.85	0.05	<0.01	<0.01	<0.01
(v)	0.80	0.50	0.35	1.55	0.10	0.15	<0.01	0.80	0.18	<0.01	<0.01	<0.01
(w)	1.10	0.60	0.35	1.55	0.10	0.25	<0.01	0.80	0.18	<0.01	<0.01	<0.01
(x)	1.10	0.65	0.45	1.55	0.15	0.25	<0.01	0.80	0.18	0.25	<0.01	<0.01
(y)	1.10	0.65	0.45	1.55	0.15	0.25	<0.01	0.80	0.18	<0.01	0.20	<0.01
(z)	1.10	0.65	0.45	1.55	0.15	0.25	<0.01	0.80	0.18	<0.01	<0.01	0.25

Example 1

This Example 1 is an example about the stability of the skin material and the structure of the core material by the heat cladding conditions.
As a skin material 10 a and 10 b, an ingot made of the alloys Nos. (a), (c), (f) and (j) shown in Table 1 and manufactured by a semi-continuous casting method was subjected to hot rolling, intermediate annealing at 370° C.×4 h, then cold rolling and intermediate annealing if needed, to thereby obtain a material having a thickness t1 of 0.20 mm.
As for the inventive examples Nos. 1 to 10 and the comparative examples Nos. 11 to 19, and 21 shown in Table 2, using the aforementioned clad material manufacturing apparatus 1, a three-layered heat rolled clad material 12 with the skin materials 10 a and 10 b clad on both surfaces of the core material 11 was manufactured.
In detail, in the state in which the skin materials 10 a and 10 b whose reference sign is shown in Table 2 were set and rotated with the skin material 10 a and 10 b contacting the peripheral surface of the cooling rollers 2 a and 2 b, the molten metal M having the core material compositions (b), (d), (e), (g), (h), (i) and (k) shown in Table 2 was poured from the above. At this time, the target thickness of the core material 11 after the heat roll cladding was set to 4.0 mm. Moreover, the contact distance L1 from the contact starting point P1 where the aforementioned skin material 10 a (10 b) begins to come into contact with the cooling roller 2 a (2 b) to the meeting point P2 where the skin material begins to come into contact with the molten metal M was set to 100 or 150 times of the thickness t1 of skin material 10 a (10 b) in the Inventive examples Nos. 1 to 10, and set to 50 or 80 times of the thickness t1 of the skin material 10 a (10 b) in the comparative examples Nos. 11 to 19, and 21. Although the pouring temperature of the molten metal M was different depending on the composition of the core material 11, in order to prevent dissolution of the skin material 10 a (10 b), it was set such that it became higher than the solidification start temperature by about 5 to about 30° C. Moreover, the peripheral speed of the cooling roller 2 a (2 b) was set to 30 m/min.
About the manufactured three-layered clad materials 12, the skin material breakage and the skin material melting ratio were evaluated by the following standard, and the average dendrite secondary arm spacing (DAS) of the core material was also measured. These results are shown in Table 2.
(Skin Material Breakage)
In the case where there was a breakage during the manufacturing the three-layered clad material 12 of 100 m length, it was noted as “yes,” and in the case where there was no breakage, it was noted as “no.” A skin material noted as “no” skin material breakage was evaluated as a good article.
(Skin Material Melting Rate)
The skin material melting rate was expressed by percentage obtained by performing five-point sampling from the organization observation of the cross-section of the hot rolled clad plate and averaging the five maximum values of the molten portions of the skin material and then dividing the average value by the original thickness of the skin material. Here, it was calculated under the assumption that there was no area reduction of the skin material due to rolling. In the case where the skin material melting rate was 5% or less, it was evaluated as a good article.
(Average DAS)
An arbitrary length L parallel to the dendrite principal axis was obtained as an average value by performing five point measurements at the value by divided by the number N of the secondary arm which exists therein. In the case where the average DAS was 10 μm less was estimated as a good article.
Subsequently, after cold rolling each hot rolled clad material 12 into a thickness of 110 μm, heat treating of 600° C.×10 min. was performed. This heat treating was heat-treatment supposing brazing. As for the inventive example No. 6 and the comparative example No. 16, they were subjected to heat treating of 170° C.×5 h. As for the inventive example No. 9 and the comparative example No. 19, they were subjected to heat treating of 120° C.×3 h. The heat treatment was a post-aging treatment intended to improve the strength of the core material.
About the clad material after the aforementioned cold rolling and heat treating, the tensile strength at ordinary temperature and the tensile strength after holding at 180° C.×10 h were measured. These results are shown in Table 2.
On the other hand, as for the comparative example No. 20 shown in Table 2, the core material had the composition (b) and the skin material had the composition (f) shown in Table 1. Initially, the ingot manufactured by the semi-continuous casting method was subjected to pre-heating and hot rolling after cutting the surface portion. The skin material having a thickness of 20 mm and the core material having a thickness of 400 mm after the surface cutting of the ingot surface were hot rolled to thereby obtain a hot rolled plate having a total thickness of 5 mm. Furthermore, the hot rolled plate with a thickness of 5 mm was cold-rolled into a thickness of 110 μm, and then subjected to heat treatment of 600° C.×10 min.

The skin material breakage, skin material melting rate, and core material average DAS of the hot rolled plate was evaluated. The skin material breakage and the skin material melting rate were evaluated by the same method as in the aforementioned invention. The core material average DAS was the value of the central portion of the ingot (400 mm thickness) having the composition (b) to be used as a core material. Moreover, as to the cold rolled plate with a thickness of 110 mm, the tensile strength after 10 hours holding at ordinary temperature and 180° C. was measured. These results are shown in Table 2.

	TABLE 2


	Hot rolled clad material	Cold rolling

Clad

Material composition (three layered clad)

Total thickness

Heat treatment

material	Skin/core/	Thickness of the	Targeted thickness		of after the cold	Heating	Late aging
No.	skin	skin t1 (mm)	of the core (mm)	L1/t1	rolling (μm)	conditions	conditions

Invention	1	(a)(b)(a)	0.20	4.0	100	110	600° C. × 10 min	—
	2	(c)(b)(c)	0.20	4.0	100	110		—
	3	(f)(d)(f)	0.20	4.0	100	110		—
	4	(f)(e)(f)	0.20	4.0	100	110		—
	5	(j)(e)(j)	0.20	4.0	100	110		—
	6	(f)(g)(f)	0.20	4.0	100	110		170° C. × 5 h
	7	(f)(h)(f)	0.20	4.0	100	110		—
	8	(f)(i)(f)	0.20	4.0	100	110		—
	9	(f)(k)(f)	0.20	4.0	100	110		120° C. × 3 h
	10	(a)(b)(a)	1.20	4.0	150	110		—
Comp.	11	(a)(b)(a)	0.20	4.0	50	110	600° C. × 10 min	—
	12	(c)(b)(c)	0.20	4.0	50	110		—
	13	(f)(d)(f)	0.20	4.0	50	110		—
	14	(f)(e)(f)	0.20	4.0	50	110		—
	15	(j)(e)(j)	0.20	4.0	50	110		—
	16	(f)(g)(f)	0.20	4.0	50	110		170° C. × 5 h
	17	(f)(h)(f)	0.20	4.0	50	110		—
	18	(f)(i)(f)	0.20	4.0	50	110		—
	19	(f)(k)(f)	0.20	4.0	50	110		120° C. × 3 h

	20	(f)(b)(f)	20/400/200 mm, hot roll clad	110		—
			into total thickness of 5 mm

	21	(a)(b)(c)	0.20	4.0	80	110		—

Clad

Quality of heat rolled clad material

Tensile strength

material	Skin	Skin melting	Core average	Normal temp.	180° C.
No.	breakage	rate (%)	DAS (μm)	strength (MPa)	strength (MPa)

Invention	1	No	<1	5.2	110	65
	2	No	<1	4.8	115	67
	3	No	3	3.8	135	78
	4	No	3	4.2	145	82
	5	No	<1	4.4	143	80
	6	No	2	6.0	125	75
	7	No	3	6.5	180	110
	8	No	3	6.2	210	170
	9	No	3	5.5	480	210
	10	No	<1	4.9	111	66
Comp.	11	Yes	6	12.4	98	59
	12	Yes	6	13.2	102	60
	13	Yes	20	11.3	115	70
	14	Yes	22	11.5	120	72
	15	Yes	7	12.0	118	69
	16	Yes	14	16.3	120	72
	17	Yes	12	14.9	175	104
	18	Yes	13	15.5	180	111
	19	No	7	13.8	410	195
	20	Yes	6	25.2	75	48
	21	Yes	6	11.5	110	60

From the result shown in Table 2, it was confirmed that in each invention manufactured by the method of the present invention the skin material was not broken, there was very few melting of the skin material, and it was stably manufactured. Moreover, in the manufactured clad material, it was confirmed that the average DAS was 10 μm or less, and it was excellent in high temperature strength.

Example 2

This Example 2 is an example about brazing performance and corrosion resistance by the skin material components and the skin material.
As a skin material 10 a and 10 b, an ingot manufactured from the alloys Nos. (m) to (r) in Table 1 by a semi-continuous casting method was subjected to hot rolling, intermediate annealing at 370° C.×4 h, then cold rolling and intermediate annealing if needed, to thereby obtain a material having a thickness t1 of 0.35 mm.
About the inventive examples Nos. 22 to 29 shown in Table 3, using the alloy having the composition shown in Table 1 as molten metal M to be used as a core material, a three-layered clad material 12 in which skin materials 10 a and 10 b were pressure-bonded to the both surfaces of the core material 11 using the aforementioned apparatus 1 for manufacturing a clad material according to the example 1 was manufactured. In manufacturing, the target thickness of the core material 11 after the hot roll cladding was set to 5.0 mm. The contact distance L1 from the contact starting point P1 to the cooling roller 2 a (2 b) of the aforementioned skin material 10 a (10 b) to the meeting point P2 where the skin material comes into contact with the molten metal M was set to 200 times of the thickness t1 of skin material 10 a (10 b). The remaining conditions were set to the same as in Example 1.
Subsequently, each heat rolled clad material 12 was cold-rolled into a thickness of 110 μm, and then subjected to a heat treatment of 600° C.×10 min.
About the clad material after the cold rolling and heat treatment, the tensile strength at ordinary temperature, the tensile strength after 180° C.×10 h holding, breakage of the skin material, melting rate of the skin material, the quality of hot rolled clad material with an average DAS were measured or evaluated. These results are shown in Table 3.
Moreover, as to the cold-rolled three-layered clad material 12, the brazing performance and the corrosion resistance were evaluated by the following method.
(Brazing Performance)
As to the inventive examples No. 22, 24, 25, 28 and 29 using (m), (n), and (o) as a skin material, using the aluminum alloy having the composition (s) shown in Table 1, it was rolled into a sheet having a thickness of 80 μm and processed into the fin 20 shown in FIG. 2. Moreover, as to the inventive examples Nos. 23, 26 and 27 using (p), (q) and (r) as a skin material, a three-layered clad material (5 μm/70 μm/5 μm, the total thickness of 80 μm) having compositions (n), (s) and (n) shown in Table 1 was manufactured, and then processed into the fin 20 shown in FIG. 2 in the same manner as mentioned above. Each of the aforementioned fins (20) had a fin thickness (Ft): 80 μm, a fin pitch (Fp): 2.0 mm and a fin height (Fh): 8 mm.
And as shown in FIG. 2, fins 20 and 20 were attached to both surfaces of the aforementioned three-layered clad material 12, and flux was applied thereto. Then, they were subjected to a brazing test by heating at 600° C.×10 min.
About these brazed articles, the junction rate and erosion were investigated. In the evaluation of the junction rate, the length that the fin 20 was detached was measured by cutting the fin, and calculated by the following formula: [1−(fin detached length)/(the entire fin joining portion)]×100. In the case where the calculated result was 80% or more, it was shown as “∘.” In the case where the calculated result was less than 80%, it was shown as “x.” In the erosion valuation, in cases where the erosion depth was less than 20 μm, it was shown as “∘,” and in cases where the erosion depth exceeded 20 μm, it was shown as “x.”
(Corrosion Resistance)
A brazed article constituted by the three-layered clad material 12 and fin 20 subjected to the brazing test was subjected to SWAAT Test (Synthetic sea Water Acetic Acid salt spray Test) defined in ASTM-G85-A3 to investigate generation of apertures and fin detaching performances. The test conditions were as follows. Corrosion test liquid adjusted so as to be pH3 by adding acetic acid to artificial seawater according to ASTM D1141 was used. A cycle of spraying the corrosion test liquid against the article for 0.5 hours and holding the article for 1.5 hours under the wet condition was repeated for 960 hours.

In evaluating the generation of pitting corrosion, in cases where no through-hole was formed in the clad material 12 after 960 hours, it was noted as “∘,” and in cases where through-holes were formed, it was noted as “x.” In evaluating the fin detachment, the sample fin subjected to the corrosion test was cut, and the similar evaluation as in the joint rate was performed. As a result, in cases where the rate was 80% or more, it was noted as “∘,” and in cases where the rate was less than 80%, it was noted “x.”

	TABLE 3


	Hot rolled clad material

Material composition (three layered clad)

Cold rolling

Clad

Targeted

Total thickness

Tensile strength

material		Thickness of the	thickness of		of after the cold	Heat treatment	Normal temp.	180° C.
No.	Skin/core/skin	skin t1 (mm)	the core (mm)	L1/t1	rolling (μm)	Heating conditions	strength (MPa)	strength (MPa)

Invention	22	(n)(l)(n)	0.35	5.0	200	110	600° C. × 10 min	140	80
	23	(q)(l)(q)	0.35	5.0	200	110		135	78
	24	(m)(l)(m)	0.35	5.0	200	110		137	78
	25	(o)(l)(o)	0.35	5.0	200	110		142	83
	26	(p)(l)(p)	0.35	5.0	200	110		130	78
	27	(r)(l)(r)	0.35	5.0	200	110		135	82
	28	(n)(l)(n)	0.01	5.0	200	110		140	80
	29	(n)(l)(n)	0.50	5.0	200	110		130	77

Clad

Brazing performance

Corrosion resistance

Quality of hot rolled clad material

material	Joining		Generation	Fin	Breakage of	Melting rate of	Average DAS of
No.	rate	Erosion	of aperatures	detachment	skin material	skin material (%)	skin material (μm)

Invention	22	∘	∘	∘	∘	No	<1	4.0
	23	∘	∘	∘	∘	No	<1	4.4
	24	x	∘	∘	∘	No	<1	4.2
	25	∘	x	∘	∘	No	<1	3.8
	26	∘	∘	x	∘	No	<1	4.6
	27	∘	∘	∘	x	No	<1	4.8
	28	∘	∘	∘	∘	No	<1	3.6
	29	∘	∘	∘	∘	No	<1	5.0

From the result shown in Table 3, it was confirmed that by using the aluminum alloy of the predetermined composition as a skin material outstanding brazing performance and corrosion resistance could be obtained. It was further confirmed that breakage of the skin material, melting rate of the skin material and average DAS of the skin material in each clad material were excellent.

Example 3

This example 3 is an example about an evaluation of the strength by the core material composition.
As a skin material 10 a and 10 b, an ingot manufactured from the alloy No. (t) in Table 1 by a semi-continuous casting method was subjected to hot rolling, intermediate annealing at 370° C.×4 h, then cold rolling and intermediate annealing if needed, to thereby obtain a material having a thickness t1 of 0.25 mm.
About the inventive examples Nos. 30 to 35 shown in Table 4, using the alloys having compositions (u) to (z) shown in Table 1 as molten metal M to be used as a core material, a three-layered clad material 12 in which skin materials 10 a and 10 b were pressure-bonded to the both surfaces of the core material 11 using the aforementioned apparatus 1 for manufacturing a clad material according to the example 1 was manufactured. In manufacturing, the target thickness of the core material 11 after the hot roll cladding was set to 5.0 mm. The contact distance L1 from the contact starting point P1 to the cooling roller 2 a (2 b) of the aforementioned skin material 10 a (10 b) to the meeting point P2 where the skin material comes into contact with the molten metal M was set to 200 times of the thickness t1 of skin material 10 a (10 b). The remaining conditions were set to the same as in Example 1.
Subsequently, each heat rolled clad material 12 was cold-rolled into a thickness of 110 μm, and then subjected to a heat treatment of 600° C.×10 min.

About the clad material after the cold rolling and heat treatment, the tensile strength at ordinary temperature and the tensile strength after 180° C.×10 h holding, the quality of the hot rolled clad material, the brazing performance, and the corrosion resistance were measured. These results are shown in Table 4.

	TABLE 4


	Hot rolled clad material

Material composition (three layered clad)

Cold rolling

Clad

Targeted

Total thickness

Tensile strength

Invention	30	(t)(v)(t)	0.25	5.0	200	110	600° C. × 10 min	87	53
	31	(t)(w)(t)	0.25	5.0	200	110		92	58
	32	(t)(x)(t)	0.25	5.0	200	110		143	86
	33	(t)(y)(t)	0.25	5.0	200	110		134	81
	34	(t)(z)(t)	0.25	5.0	200	110		152	92
	35	(t)(u)(t)	0.25	5.0	200	110		65	38

Clad

Brazing performance

Corrosion resistance

Quality of hot rolled clad material

material	Joining		Generation	Fin	Breakage of	Melting rate of	Average DAS of
No.	rate	Erosion	of apertures	detachment	skin material	skin material (%)	skin material (μm)

Invention	30	∘	∘	∘	∘	No	2	3.8
	31	∘	∘	∘	∘	No	2	4.0
	32	∘	∘	∘	∘	No	3	4.2
	33	∘	∘	∘	∘	No	3	4.8
	34	∘	∘	∘	∘	No	3	4.4
	35	∘	∘	∘	∘	No	2	3.8

From the result shown in Table 4, it was confirmed that by using the aluminum alloy of the predetermined composition as a core material outstanding high temperature strength could be obtained. Furthermore, it was confirmed that the breakage of the skin material, the melting rate of the skin material, the average DAS of the core material, the brazing performance and the corrosion resistance were excellent.
(Workability)
About each of the clad materials shown in Table 5 among the clad materials shown in Tables 2, 3 and 4, the workability was evaluated based on the formability when the clad material was formed by roll forming into a fin (20) shape as follows. In cases where it was formed into a preferable shape, it was noted as “⊚”, in cases where it was formed into a fin shape although there were variations in fin shape dimension, it was noted as “∘,” and in cases where it was impossible to form into a fin shape due to an occurrence of breakage, it was noted as “x”.

TABLE 5

Clad material No. Workability

Inventive article 1 ⊚

4 ◯

Comparative article 11 X

12 X

Inventive article 22 ◯

30 ⊚

31 ⊚

32 ◯

33 ◯

34 ◯

35 ⊚
From the results shown in Table 5, it was confirmed that the clad materials according to the present invention was superior to the comparative articles in workability. Furthermore, it was also confirmed that the inventive articles not exhibited excellent tensile strength or brazing performance in Tables 2 to 4 were superior to comparative articles in workability.
In the above-mentioned Examples 1 to 3, the thickness t1 of the skin material 10 a (10 b) was not changed while the skin materials 10 a and 10 b were being clad onto the core material 11. However, the present invention is not limited to it. The present invention also includes the case in which the thickness of the skin material decreases due to the cladding by receiving a slight rolling pressure together with the core material when the skin materials passes through the cooling rollers 2 a and 2 b.

INDUSTRIAL APPLICABILITY

The clad material manufactured by the present invention includes a core material and skin materials clad on the both surfaces of the core material, wherein the composition of the skin material is different from that of the core material. The clad material can be used for manufacturing metallic material to which the aforementioned characteristics were given by cladding brazing material or corrosion resistance material as skin material.
While the present invention may be embodied in many different forms, a number of illustrative embodiments are described herein with the understanding that the present disclosure is to be considered as providing examples of the principles of the invention and such examples are not intended to limit the invention to preferred embodiments described herein and/or illustrated herein.
While illustrative embodiments of the invention have been described herein, the present invention is not limited to the various preferred embodiments described herein, but includes any and all embodiments having equivalent elements, modifications, omissions, combinations (e.g., of aspects across various embodiments), adaptations and/or alterations as would be appreciated by those in the art based on the present disclosure. The limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the present specification or during the prosecution of the application, which examples are to be construed as non-exclusive. For example, in the present disclosure, the term “preferably” is non-exclusive and means “preferably, but not limited to.” In this disclosure and during the prosecution of this application, means-plus-function or step-plus-function limitations will only be employed where for a specific claim limitation all of the following conditions are present in that limitation: a) “means for” or “step for” is expressly recited; b) a corresponding function is expressly recited; and c) structure, material or acts that support that structure are not recited. In this disclosure and during the prosecution of this application, the terminology “present invention” or “invention” may be used as a reference to one or more aspect within the present disclosure. The language present invention or invention should not be improperly interpreted as an identification of criticality, should not be improperly interpreted as applying across all aspects or embodiments (i.e., it should be understood that the present invention has a number of aspects and embodiments), and should not be improperly interpreted as limiting the scope of the application or claims. In this disclosure and during the prosecution of this application, the terminology “embodiment” can be used to describe any aspect, feature, process or step, any combination thereof, and/or any portion thereof, etc. In some examples, various embodiments may include overlapping features. In this disclosure and during the prosecution of this case, the following abbreviated terminology may be employed: “e.g.” which means “for example;” and “NB” which means “note well.”

Claims

1. A method for manufacturing a clad material, comprising the steps of:

continuously supplying molten metal into a gap between a pair of cooling rollers to cast a core material; and

cladding skin materials on both surfaces of the core material with hot rolling by continuously supplying the skin materials on peripheral surfaces of the cooling rollers so that the skin materials prevent direct contact between the cooling rollers and the molten metal,

wherein the skin materials are supplied so as to come into contact with the peripheral surfaces of the cooling rollers, and

wherein a contact distance (L1) from a contact starting point (P1) where the skin material begins to come into contact with the cooling roller to a meeting point (P2) where the skin material begins to come into contact with the molten metal is set to 100 times or more of a thickness (t1) of the skin material.

2. The method for manufacturing a clad material as recited in claim 1, wherein the core material and the skin material are made of aluminum or its alloy.

3. The method for manufacturing a clad material as recited in claim 1, wherein the thickness (t1) of the skin material is 20 to 400 μm.

4. The method for manufacturing a clad material as recited in claim 2, wherein at least one of the skin materials is made of Al—Si series alloy.

5. The method for manufacturing a clad material as recited in claim 4, wherein the Al—Si series alloy consists essentially of

Si: 5 to 15 mass %,

Fe: 0.05 to 0.6 mass %,

Cu: 0.01 to 0.6 mass %,

Mn: 0.01 to 0.8 mass %,

Mg: 0.01 to 0.2 mass %,

Ti: 0.01 to 0.2 mass %, and

the balance being Al and inevitable impurities.

6. The method for manufacturing a clad material as recited in claim 2, wherein at least one of the skin materials is made of Al—Zn series alloy.

7. The method for manufacturing a clad material as recited in claim 6, wherein the Al—Zn series alloy consists essentially of

Si: 0.05 to 0.6 mass %,

Fe: 0.05 to 0.6 mass %,

Cu: 0.01 to 0.6 mass %,

Mn: 0.01 to 0.8 mass %,

Mg: 0.01 to 0.2 mass %,

Ti: 0.01 to 0.2 mass %,

Zn: 0.35 to 8.5 mass %, and

the balance being Al and inevitable impurities.

8. The method for manufacturing a clad material as recited in claim 1, wherein a thickness (t2) of the skin material after hot roll cladding is 0.5 to 8 mm.

9. The method for manufacturing a clad material as recited in claim 2, wherein the molten metal to become the core material consists essentially of

Si: 0.05 to 1.5 mass %,

Fe: 0.05 to 2 mass %,

Cu: 0.05 to 0.8 mass %,

Mn: 0.15 to 2.8 mass %,

at least one of elements selected from the group consisting of Cr: 0.03 to 0.7 mass %, Mg: 0.01 to 0.2 mass %, Ti: 0.01 to 0.3 mass %, and Zn: 0.01 to 1.5 mass %, and

the balance being Al and inevitable impurities.

10. The method for manufacturing a clad material as recited in claim 9, wherein the molten metal further includes at least one of elements selected from the group consisting of Zr: 0.15 to 1.5 mass %, V: 0.03 to 1.5 mass %, and Sc: 0.02 to 0.5 mass %.

11. The method for manufacturing a clad material as recited in any one of claims 1 to 10, wherein cold rolling is performed after the hot roll cladding.

12. A clad material in which skin materials are clad on both surfaces of a core material, wherein the clad material is manufactured by the steps of continuously supplying molten metal into a gap between a pair of cooling rollers to cast a core material, and cladding skin materials on both surfaces of the core material with hot rolling by continuously supplying the skin materials on peripheral surfaces of the cooling rollers so that the skin materials prevent direct contact between the cooling rollers and the molten metal, wherein the skin materials are supplied so as to come into contact with the peripheral surfaces of the cooling rollers, and wherein a contact distance (L1) from a contact starting point (P1) where the skin material begins to come into contact with the cooling roller to a meeting point (P2) where the skin material begins to come into contact with the molten metal is set to 100 times or more of a thickness (t1) of the skin material.

13. The clad material as recited in claim 12, wherein the clad material is cold rolled after the hot roll cladding.

14. The clad material as recited in claim 12, wherein an average spacing of a dendrite secondary arm spacing of the core material formed by the heat roll cladding is 0.1 to 10 μm

15. The clad material as recited in any one of claims 12 to 14, wherein the clad material is heat exchanger component material.

16. An apparatus for manufacturing a clad material, comprising:

a pair of cooling rollers for continuously casting molten metal passing through a gap formed between the cooling rollers;

a molten metal supplying portion for supplying the molten metal to become a core material into the gap; and

a skin material supplying portion for supplying a skin material on a peripheral surface of the cooling roller and making the skin material come into contact with the peripheral surface of the cooling roller before the skin material joins the molten metal,

wherein the cooling rolls are rotated while continuously supplying the molten metal and the skin material to the cooling rolls to thereby continuously clad the skin materials to both surfaces of the core material.