CA2763153C - Brazing method for joining using amorphous sputtered coating layer as filler and amorphous brazing filler for the brazing method - Google Patents
Brazing method for joining using amorphous sputtered coating layer as filler and amorphous brazing filler for the brazing method Download PDFInfo
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- CA2763153C CA2763153C CA2763153A CA2763153A CA2763153C CA 2763153 C CA2763153 C CA 2763153C CA 2763153 A CA2763153 A CA 2763153A CA 2763153 A CA2763153 A CA 2763153A CA 2763153 C CA2763153 C CA 2763153C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
- G21C3/30—Assemblies of a number of fuel elements in the form of a rigid unit
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Materials Engineering (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
Abstract
Disclosed herein is a brazing method for joining using an amorphous sputtered coating layer as a filler, the method comprising forming an amorphous coating layer through a sputter coating on a joining part between base metals (Step 1); and heating the joining part of Step 1 (Step 2).
When the multi-component amorphous inserting alloy according to the present invention is coated on the surface of base metals using a sputtering method that is one of a physical vapor depositions, there are effects such that the multi-component target composition can be intactly maintained on the coating layer of base metals; the uniformity of inserting layer according to the positions, such as, the precise thickness control and the uniform applying of base metals surface can be secured; and also perfect interface contact can be performed to secure the uniformity and reproducibility of the joint part when joining.
When the multi-component amorphous inserting alloy according to the present invention is coated on the surface of base metals using a sputtering method that is one of a physical vapor depositions, there are effects such that the multi-component target composition can be intactly maintained on the coating layer of base metals; the uniformity of inserting layer according to the positions, such as, the precise thickness control and the uniform applying of base metals surface can be secured; and also perfect interface contact can be performed to secure the uniformity and reproducibility of the joint part when joining.
Description
BRAZING METHOD FOR JOINING USING AMORPHOUS SPUTTERED COATING
LAYER AS FILLER AND AMORPHOUS BRAZING FILLER FOR THE BRAZING
METHOD
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a brazing method for joining using an amorphous sputtered coating layer as a W filler, and an amorphous brazing filler for the brazing method.
LAYER AS FILLER AND AMORPHOUS BRAZING FILLER FOR THE BRAZING
METHOD
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a brazing method for joining using an amorphous sputtered coating layer as a W filler, and an amorphous brazing filler for the brazing method.
2. Description of the Related Art Most structures, that is, a building, a transport equipment, such as an automobile, a ship, an aircraft, a train, and the like, all kinds of pipings, pipes, and the like, have many equipment parts that need a joining between metals or alloys, and high-temperature fusion welding way using Arc welding technique is mostly used for the joining between metals and alloys. However, the fusion welding (or welding) process has a limitation that mechanical properties are deteriorated by changing the structures of the surrounding base metals, such as a particle coarsening, a formation of heat affected zone, and the like due to a high-temperature operation, and also a material defect, such as a stress corrosion cracking, and the like, is generated due to a formation of internal stress by a high-temperature treating.
W In addition, there is a limitation that in the case of the parts that need the joining of the thin-thickness or broad-side as a shape, and a high-temperature structure, the modification or erosion of base metal may be occurred so that it is difficult to apply with the high-temperature welding process. The above aspects considered, currently, the studies about low-temperature solid-state welding technique using non-fusion way are now actively proceeding, in which for the non-fusion way, the base metal is not molten, and the low-temperature solid-state welding technique gives sufficient tensile strength and adhesive strength between metals and alloys of the structure parts, and an excellent prevention property of leakage.
The studies for applying a brazing technique that is one of the solid-state welding techniques to the joining of dissimilar metals, ceramics, high-temperature special materials, and the like, are actively proceeding, in which the dissimilar metals, the ceramics, the high-temperature special materials, and the like is impossible to join each other using the fusion joining technique. The studies for applying the brazing technique for all sorts of the parts for the high-tech core industry facilities are proceeding because the brazing technique not changes the base metals, and has a preferable effect on the aspect of heat stress of joint while it does not effect to the mechanical properties. Especially, the solid-state joining technique, such as, the brazing, is applied to a nuclear fuel tube that is one of core parts of nuclear reactor for a nuclear industry, in which the nuclear fuel tube has the thickness of very thin, i.e., not more than 0.4 mm so that the base metals of the nuclear fuel tube are modified and eroded when using the high-temperature joining technique.
Korean Patent Application Publication No. 2008-7006740 relates to amoLphous iron-nickel containing brazing foil and brazing method, and more specifically, to an iron-nickel containing brazing foil and brazing method, in which the amorphous soft brazing foil has the composition including 25 5 a 5 50 atom%; 25 < b < 50 atom%; 5 < c 5 15 atom%; 4 5 d 5 15 atom%; 4 5 e 5 15 atom%; 0 5 f 5 5 atom%; 0 < g 5 6 atom96; and additional impurities, where 10 5 d+e+g 5 28 atom% and
W In addition, there is a limitation that in the case of the parts that need the joining of the thin-thickness or broad-side as a shape, and a high-temperature structure, the modification or erosion of base metal may be occurred so that it is difficult to apply with the high-temperature welding process. The above aspects considered, currently, the studies about low-temperature solid-state welding technique using non-fusion way are now actively proceeding, in which for the non-fusion way, the base metal is not molten, and the low-temperature solid-state welding technique gives sufficient tensile strength and adhesive strength between metals and alloys of the structure parts, and an excellent prevention property of leakage.
The studies for applying a brazing technique that is one of the solid-state welding techniques to the joining of dissimilar metals, ceramics, high-temperature special materials, and the like, are actively proceeding, in which the dissimilar metals, the ceramics, the high-temperature special materials, and the like is impossible to join each other using the fusion joining technique. The studies for applying the brazing technique for all sorts of the parts for the high-tech core industry facilities are proceeding because the brazing technique not changes the base metals, and has a preferable effect on the aspect of heat stress of joint while it does not effect to the mechanical properties. Especially, the solid-state joining technique, such as, the brazing, is applied to a nuclear fuel tube that is one of core parts of nuclear reactor for a nuclear industry, in which the nuclear fuel tube has the thickness of very thin, i.e., not more than 0.4 mm so that the base metals of the nuclear fuel tube are modified and eroded when using the high-temperature joining technique.
Korean Patent Application Publication No. 2008-7006740 relates to amoLphous iron-nickel containing brazing foil and brazing method, and more specifically, to an iron-nickel containing brazing foil and brazing method, in which the amorphous soft brazing foil has the composition including 25 5 a 5 50 atom%; 25 < b < 50 atom%; 5 < c 5 15 atom%; 4 5 d 5 15 atom%; 4 5 e 5 15 atom%; 0 5 f 5 5 atom%; 0 < g 5 6 atom96; and additional impurities, where 10 5 d+e+g 5 28 atom% and
3 FeaNibCreSidBeM0fPg, a+b+c+d+e+f+g=100. An excellent brazed joint can be prepared by using the brazing foil. However, there is a limitation that when filler in a type of the brazing foil or ribbon is used, a precise control of thickness is difficult so that the non-uniformity of filler thickness is caused and then the non-uniformity of joint may be caused after joining.
Korean Patent No. 10-0597310 relates to a manufacturing method of an attachment with Zr-Be alloy layer and a fusion brazing joining process of nuclear fuel rod for heavy-water W reactor by using the attachment. An object of the above invention is to suppress a delaminating of depositing layer and a beryllium steam that can be generated when brazing due to not use of a pure beryllium as a filler metal like the prior art when joining an attachment (support, loose spacing body, button, and the like) on the surface of nuclear fuel rod that consists a nuclear fuel bundle for the safety of workers and the prevention of environment pollution, and also additionally is to improve a production yield of nuclear fuel rod by decreasing a production loss rate of attachment and nuclear fuel rod to be wasted that are generated by detaching the attachment after brazing. However, there is a limitation that for the brazing process, the joining is proceeded at high temperature, i.e., above 1050 00 so that the control of joint thickness is difficult due to an erosion of base metals when
Korean Patent No. 10-0597310 relates to a manufacturing method of an attachment with Zr-Be alloy layer and a fusion brazing joining process of nuclear fuel rod for heavy-water W reactor by using the attachment. An object of the above invention is to suppress a delaminating of depositing layer and a beryllium steam that can be generated when brazing due to not use of a pure beryllium as a filler metal like the prior art when joining an attachment (support, loose spacing body, button, and the like) on the surface of nuclear fuel rod that consists a nuclear fuel bundle for the safety of workers and the prevention of environment pollution, and also additionally is to improve a production yield of nuclear fuel rod by decreasing a production loss rate of attachment and nuclear fuel rod to be wasted that are generated by detaching the attachment after brazing. However, there is a limitation that for the brazing process, the joining is proceeded at high temperature, i.e., above 1050 00 so that the control of joint thickness is difficult due to an erosion of base metals when
4 joining the attachment and nuclear fuel rod tube with very thin thickness of 0.4 mm. In addition, there is a limitation that in the terms of the physical properties of the joint, a undesired micro structure is formed due to the formation of harmful state, such as an intermetallic compound so that the physical properties, such as a corrosion, a strength, and the like are deteriorated.
Recently, there is a rising interest on low-temperature brazing technique using low-melting amorphous filler in the case of zirconium, titanium ally, and the like, and also on the inserting technique of amorphous filler when joining in order to secure uniformity.
For this reason, the present inventors developed a method for brazing a multi-component amorphous alloy having low-temperature melting point, and filler for the method, and confirmed that the present invention is an effective brazing method to a precise thickness control and uniform surface component.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a brazing method for joining using an amorphous sputtered coating layer as a filler.
Another object of the present invention is to provide an amorphous brazing filler for the method.
Recently, there is a rising interest on low-temperature brazing technique using low-melting amorphous filler in the case of zirconium, titanium ally, and the like, and also on the inserting technique of amorphous filler when joining in order to secure uniformity.
For this reason, the present inventors developed a method for brazing a multi-component amorphous alloy having low-temperature melting point, and filler for the method, and confirmed that the present invention is an effective brazing method to a precise thickness control and uniform surface component.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a brazing method for joining using an amorphous sputtered coating layer as a filler.
Another object of the present invention is to provide an amorphous brazing filler for the method.
5 The present invention provides a brazing method for joining using an amorphous sputtered coating layer as a filler, the method including: forming an amorphous coating layer through a sputter coating on a joining part between joining base metals (Step 1); and heating the joining part of Step 1 (Step 2).
In addition, the present invention provides an amorphous brazing filler used for the joining method. The amorphous brazing filler includes Zr-Ti-x-y or Zr-Ti-x-y-z where x, y, W and z are respectively selected from the group consisting of alloy atoms including Cu, Ni, Fe, Al, Sn, and Be, respectively, and x, y, and z are not identical in order to achieve the objects as mentioned above.
When the multi-component amorphous inserting alloy according to the present invention is coated on the surface of base metals using a sputtering method that is one of a physical vapor depositions, there are effects such that the multi-component target composition can be intactly maintained on the coating layer of base metals; the uniformity of inserting layer according to the positions, such as, the precise thickness control and the uniform applying of base metals surface can be secured; and also perfect interface contact can be perfoLmed to secure the uniformity and reproducibility of the joint part when joining. In addition, the filler according to the present invention has effective on
In addition, the present invention provides an amorphous brazing filler used for the joining method. The amorphous brazing filler includes Zr-Ti-x-y or Zr-Ti-x-y-z where x, y, W and z are respectively selected from the group consisting of alloy atoms including Cu, Ni, Fe, Al, Sn, and Be, respectively, and x, y, and z are not identical in order to achieve the objects as mentioned above.
When the multi-component amorphous inserting alloy according to the present invention is coated on the surface of base metals using a sputtering method that is one of a physical vapor depositions, there are effects such that the multi-component target composition can be intactly maintained on the coating layer of base metals; the uniformity of inserting layer according to the positions, such as, the precise thickness control and the uniform applying of base metals surface can be secured; and also perfect interface contact can be perfoLmed to secure the uniformity and reproducibility of the joint part when joining. In addition, the filler according to the present invention has effective on
6 In accordance with one aspect of the present invention, there is provided a brazing method for joining using an amorphous sputtered coating layer as a filler, the brazing method comprising: forming an amorphous coating layer through a sputter coating on a joining part between base metals (Step 1); and heating the joining part of Step 1 (Step 2), wherein the each of said base metal is a zirconium alloy, wherein the filler is Zra-Tib-Cuc-Nid containing alloy where a, W b, c, and d mean mass% of Zr, Ti, Cu, and Ni, respectively, and 30a70, 5b15, 8c_20, and 1(31d.-20.
6a brazing at low temperature due to a narrow fusion part and low-fusion temperature thereby minimizing the modification and erosion thereof.
BREIF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
Fig. 1 is a mimetic diagram of brazing using amorphous filler.
Fig. 2 is a graph showing XRD analysis result of Zr62-Ti11-Cu13-Ni14 (Example 1) alloy that is a crystalline target for a sputter coating.
Fig. 3 is a graph showing XRD analysis result of coating layer showing an amorphous structure after a sputter coating of Zr62-T111-Cu13-Ni14 (Example 1) alloy.
Fig. 4 is SEM photograph showing the surface of coating layer after a sputter coating of Zr62-Ti11-Cu13-Ni14 (Example 1) alloy.
Fig. 5 is an observation photo showing a cross-section of coating layer using an optical microscope after a sputter coating of Zr62-Ti11-Cu13-Ni3.4 (Example 1) alloy.
Fig. 6 is a graph showing the result after performing a
6a brazing at low temperature due to a narrow fusion part and low-fusion temperature thereby minimizing the modification and erosion thereof.
BREIF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
Fig. 1 is a mimetic diagram of brazing using amorphous filler.
Fig. 2 is a graph showing XRD analysis result of Zr62-Ti11-Cu13-Ni14 (Example 1) alloy that is a crystalline target for a sputter coating.
Fig. 3 is a graph showing XRD analysis result of coating layer showing an amorphous structure after a sputter coating of Zr62-T111-Cu13-Ni14 (Example 1) alloy.
Fig. 4 is SEM photograph showing the surface of coating layer after a sputter coating of Zr62-Ti11-Cu13-Ni14 (Example 1) alloy.
Fig. 5 is an observation photo showing a cross-section of coating layer using an optical microscope after a sputter coating of Zr62-Ti11-Cu13-Ni3.4 (Example 1) alloy.
Fig. 6 is a graph showing the result after performing a
7 heat analysis after a sputter coating of Zr62-Ti11-Cu13-Ni14 (Example I) alloy.
Fig. 7 is SEM photograph showing a micro structure of a joint (Example 2) using Zr62-T111-Cu13-Ni14 alloy; and Fig. 8 is SEM photograph showing a micro structure of a joint (Example 3) using Zr72-Ti7-0u8-Fe13 alloy.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Features and advantages of the present invention will be more clearly understood by the following detailed description of the present preferred embodiments by reference to the accompanying drawings. It is first noted that teLms or words used herein should be construed as meanings or concepts corresponding with the technical sprit of the present invention, based on the principle that the inventor can appropriately define the concepts of the terms to best describe his own invention. Also, it should be understood that detailed descriptions of well-known functions and structures related to the present invention will be omitted so as not to unnecessarily obscure the important point of the present invention.
Hereinafter, the present invention will be described in detail.
The present invention provides a brazing method for
Fig. 7 is SEM photograph showing a micro structure of a joint (Example 2) using Zr62-T111-Cu13-Ni14 alloy; and Fig. 8 is SEM photograph showing a micro structure of a joint (Example 3) using Zr72-Ti7-0u8-Fe13 alloy.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Features and advantages of the present invention will be more clearly understood by the following detailed description of the present preferred embodiments by reference to the accompanying drawings. It is first noted that teLms or words used herein should be construed as meanings or concepts corresponding with the technical sprit of the present invention, based on the principle that the inventor can appropriately define the concepts of the terms to best describe his own invention. Also, it should be understood that detailed descriptions of well-known functions and structures related to the present invention will be omitted so as not to unnecessarily obscure the important point of the present invention.
Hereinafter, the present invention will be described in detail.
The present invention provides a brazing method for
8 joining using a sputter coating, the brazing method including:
(Step 1) forming an amorphous coating layer through a sputter coating on a joining part between base metals; and (Step 2) heating the joining part of Step 1.
Hereinafter, the present invention will be described step-by-step in detail.
Step 1 according to the present invention is to form an amorphous coating layer through a sputter coating on a joining part between base metals. When using the conventional amorphous alloy as a filler, it was used in a type of powder using a gas atomization or as a filler after a production process in a type of amorphous ribbon or foil with a melt spinning. However, there are limitations that in the case of the foil or ribbon, a precise control of thickness is difficult to cause a non-unifoimity of filler thickness; and in the case of the powder, a precise control of particles sizes and a unifoim applying of filler on the surface of base metals are difficult when joining. On the other hand, there are advantages that when coating on the surface of base metals using a sputtering method that is one of physical vapor depositions, a multi-component target composition can be intactly maintained at the coating layer; the thickness can be controlled; it can be applied on the surface of base metals;
and also the perfect contact can be maintained on the interface so that the uniformity and reproducibility of the
(Step 1) forming an amorphous coating layer through a sputter coating on a joining part between base metals; and (Step 2) heating the joining part of Step 1.
Hereinafter, the present invention will be described step-by-step in detail.
Step 1 according to the present invention is to form an amorphous coating layer through a sputter coating on a joining part between base metals. When using the conventional amorphous alloy as a filler, it was used in a type of powder using a gas atomization or as a filler after a production process in a type of amorphous ribbon or foil with a melt spinning. However, there are limitations that in the case of the foil or ribbon, a precise control of thickness is difficult to cause a non-unifoimity of filler thickness; and in the case of the powder, a precise control of particles sizes and a unifoim applying of filler on the surface of base metals are difficult when joining. On the other hand, there are advantages that when coating on the surface of base metals using a sputtering method that is one of physical vapor depositions, a multi-component target composition can be intactly maintained at the coating layer; the thickness can be controlled; it can be applied on the surface of base metals;
and also the perfect contact can be maintained on the interface so that the uniformity and reproducibility of the
9 joint can be secured.
Additionally, there is an advantage that a coating can be uniformly performed even on the parts with a wide area or complicated shapes so that it can be used for various parts as compared with ribbon-type or foil-type filler.
For Step 1, the joining base metal is a zirconium alloy, and in this situation, filler to be coated is preferably Zr-Ti-x-y or Zr-Ti-x-y-z (here, x, y, and z are one selected from the group consisting of alloy atoms including Cu, Ni, Fe, Al, M Sn, and Be, respectively, but x, y, and z are not identical).
The zirconium alloy is zirconium to which an element, such as, Sn, Fe, Cr, Ni, Cu, Nb, and the like, is added, and includes Zircaloy-1, Zircaloy-2, Zircaloy-3, Zircaloy-4, Low tin improved Zicaloy-4, Ozhennite, and the like. The zirconium alloy is an alloy that has very improved corrosion resistance and mechanical property as compared with a pure zirconium.
Since an alloy element is generally added in less than 2-3 %, a neutron absorption cross-sectional area of alloy is only very little increased in the degree of about 0.2 barn. The zirconium alloy is used for a nuclear fuel clad tube, guide tube, spacer grid, and the like of light-water reactor and heavy-water reactor due to the above features, and mainly used for a nuclear fuel clad tube, pressure tube, Calandria Tube, and the like.
The zirconium alloy is preferably Zircaloy-4. The general composition of Zircaloy-4 that is one type of the zirconium alloy includes 1.2-1.7 wt% of Sn, 0.18-0.24 wt% of Fe, 0.07-0.13 wt% of Cr, and a zirconium residue. The zirconium alloys that are developed for more improving a corrosion resistance and a mechanical property at the same time in cooling water under the conditions of high-temperature and high-pressure are used for a nuclear fuel clad tube of light-water reactor that is mainly used in the whole world power reactors until quite recently. There are Zircaloy-2, M Zircaloy-4, and Ozhennite that are used in the former Soviet Union as a typical alloy. Among those, Zircaloy-4 is frequently used for Pressurized Water Reactor (PWR).
The filler is preferably Zra-Tib-Cuc-Nid containing alloy (a, b, c, and d mean mass% of Zr, Ti, Cu, and Ni, respectively, and 305a570, 55b515, 85c520, and 105d520), and more preferably, has Zr62-Ti11-Cu13-Ni14 alloy composition, or Zra-Tib-Cuc-Fed containing alloy (a, b, c, and d mean mass% of Zr, Ti, Cu, and Fe, respectively, and 405a580, 55b515, 55c515, and 55d515), and more preferably, has Zr72-Ti7-Cu8-Fe13 alloy composition. Since the alloy has low melting point, it has an effect in preventing erosion, a modification, and a mechanical deterioration of base metals when heat-treating for brazing.
The thickness of the filler to be coated in Step 1 is preferably 5-200 gm. There are limitations that when the thickness of the filler is below 5 M, it is not sufficient for a role as a joining material, and when the thickness of the filler exceeds 200 M, an excessive amount of filler flows out in a liquid phase when melting or a good joint structure is difficult to form.
Step 2 according to the present invention to heat to a joining part. With reference to the mimetic diagram as shown in Fig. 1, the principle of the brazing according to the W present invention is as follows. When solid filler(B) is added between the base metals(Al, A2), and then heated, the filler is melted and then liquid filler and base metals are diffused so that the joining between the filler and base metals is done due to isothermal solidification diffusion.
Meanwhile, infrared heating equipment among heat transfer equipments is known as very fast heat transfer equipment because most atomic bonds of objects are easily excitated in an infrared radiation area due to an electro-magnetic radiation. Additionally, an infrared heating has an advantage that it can heat only desired part by a direct radiation thereto using a coldwall process. Accordingly, the infrared heating with the above-explained advantages may be efficiently used for the heating of Step 2, but not limited thereto.
For Step 2, when the joining base metals is a zirconium alloy and the filler to be coated is Zra-Tib-Cuc-Nid (a, b, c, and d are mass% of Zr, Ti, Cu, and Ni, respectively, and 305a570, 55b15, 85.c20, and 10,0120), preferably the maintenance temperature is 720 - 1050 C and the maintenance period is 0.5 - 60 minutes. Since the ranges of solidus temperature and liquidus temperature of Zra-Tib-Cuc-Nid (a, b, c, and d are mass% of Zr, Ti, Cu, and Ni, respectively, and 305a570, 85-c520, and 105d520) alloy are 720 - 1050 C, to there are limitations that when the maintenance temperature is below 720 "ID, the filler is not melted so that the brazing is not performed and when the maintenance temperature exceeds 1050 C, a fine structure modification or excessive erosion is caused to the base metals.
Moreover, the maintenance temperature is more preferably minimum at least 30 ct than the melting temperature of filler when heating.
For Step 2, when the joining base metals is a zirconium alloy and the filler to be coated is zra-Tib-Cuc-Fed (a, b, c, and d are mass% of Zr, Ti, Cu, and Fe, respectively, and 405a80, 55c515, and 5c1.15), preferably the maintenance temperature is 720 - 1050 cC and the maintenance period is 0.5 - 60 minutes. Since the ranges of solidus temperature and liquidus temperature of Zra-Tib-Cuc-Fed (a, b, c, and d are mass% of Zr, Ti, Cu, and Fe, respectively, and 405a580, 551D15, 5c515, and 5ci-5_15) alloy are 720 - 1050 C, there are limitations that when the maintenance temperature is below 720 C, the filler is not melted so that the brazing is not performed and when the maintenance temperature exceeds 1050 C, a fine structure modification or excessive erosion is caused to the base metals.
Moreover, the maintenance M temperature is more preferably minimum at least 30 C than the melting temperature of filler when heating.
For Step 2, the heat treating is preferably performed under an inert atmosphere, such as, for example an argon atmosphere. There is an effect on preventing the production of impurities of alloy in the joining material by blocking the contact with oxygen during heat-treating.
The brazing method for joining according to the present invention may be usefully applied to a nuclear fuel rod of heavy-water reactor. For the brazing of nuclear fuel rod of the conventional heavy-water reactor, a beryllium is deposited and then heat is applied to join, but there was limitation that a flaking phenomenon, in which a beryllium layer is fallen out during the brazing process, is generated to cause the defect of the joint, in addition to a harmful problem of beryllium. For another method, Zr-Be alloy was prepared to use for brazing, but there was limitation that the operation should be performed at high temperature of above 1050 'C and the structural safety of the joint is not secured. Meanwhile, for the brazing method for joining using the sputter coating layer according to the present invention as a filler, there are advantages that when coating on the surface of base metals using the sputtering method that is one of physical vapor W depositions, the multi-component target composition can be intactly maintained on the coating layer of the surface of base metals; the thickness can be easily controlled; it can be uniformly applied to the surface of base metals; and also the perfect contact can be maintained on the interface.
Therefore, the unifoLmity and reproducibility of the joint can be secured.
Additionally, the present invention provides amorphous brazing filler used for the method for joining, in which the filler is Zr-Ti-x-y or Zr-Ti-x-y-z (here, x, y, and z are one selected from the group consisting of alloy elements including Cu, Ni, Fe, Al, Sn, and Be, respectively, but x, y, and z are not identical). When the alloy elements, such as, Cu, Ni, Fe, Al, Sn, and Be, are added to the zirconium alloy, the melting point of the inserting alloy is decreased so that the temperature for joining can be decreased and also the joint with the same corrosion resistance and mechanical property as the zirconium alloy that is base metals can be secured by maximizing the joint structure.
The brazing filler can be usefully applied to the zirconium alloy joining. The zirconium that consists the brazing filler has a thermal neutron absorption cross-section of 0.18 barn that is smaller than 0.23 barn of aluminum as well as about 3.2 barn of stainless steel. Moreover, it is M very suitable to use as a reactor core material of a nuclear reactor because it has excellent mechanical property and corrosion resistance and also excellent compatability with uranium dioxide (UO2) that is used as a nuclear fuel.
The filler preferably includes 30-70 wt% of Zr, 5-15 wt%
of Ti, 8-20 wt% of Cu, and 10-20 wt% of Ni, and the contents of the filler are more preferably 62 wt% of Zr, 11 wt% of Ti, 11 wt% of Cu, and 14 wt% of Ni, respectively. The melting and coagulation phenomenon are occurred in the very narrow range of temperature for the brazing filler.
Specifically, the ranges of liquidus temperature and solidus temperature of the filler that is Zr30_70-Tis-15-Cue-20-Ni10-20 according to the present invention are 720 - 950 C, and the solidus temperature is 770 00 and the liquidus temperature is 815 C in the case of the brazing filler with Zr62-Ti11-Cu13-Ni14 alloy composition.
Also, The filler preferably includes 40-80 wt% of Zr, 5-15 wt%
of Ti, 5-15 wt % of Cu, and 5-15 wt% of Fe, and the contents of the filler are more preferably 72 wt% of Zr, 7 wt% of Ti, 8 wt% of Cu, and 13 wt% of Fe, respectively. The melting and coagulation phenomenon are occurred in the very narrow range of temperature for the brazing filler.
Specifically, the ranges of liquidus temperature and solidus temperature of the filler that is Zr40-80-Ti5_15-Cu5....15-Fe5_15 according to the present invention are 720 - 1050 00, and the solidus temperature is 820 "ID and the liquidus temperature is 845 C in the case of the brazing filler with Zr72-T17-Cu8-Fe13 alloy composition. As mentioned above, there are advantages that the brazing filler has a narrow melting temperature range, so that the ununiformly melting of the filler is reduced thereby improving a flow rate and the brazing filler has a low melting temperature so that the structural modification and the decrease of the mechanical property of base metals are not caused, and also it is possible to join.
The brazing filler with Zr62-Ti11-Cu13-Ni14 alloy composition according to the present invention has low melting point as mentioned above, and it can be explained from the fact of the eutectic reaction between the component phases that consists the composition. When the content of nickel is constant as 33.3 atom% for the alloy system consisting of Zr-Ti-Ni, the component phase of zirconium-rich area is consisted of two phases of Zr2Ni and (Zr, Ti)2Ni phases and it is known that there is Zr2Ni-(Zr, Ti)2Ni binary eutectic point of 850 'C
by the eutectic reaction between the component phases, and in this situation, copper is added as a melting point depprassant to obtain more low-melting point. That is, Zr-Ti-Cu-Ni quarternary alloy composition allows to more reducing the solidus temperature and liquidus temperature by substituting a part of nickel that is included in Zr-Ti-Ni ternary alloy M composition with copper.
Therefore, there is an advantage that the structural modification and deterioration damage of base metals can be minimized by using the alloy composition as mentioned above as the brazing filler.
A bulk target preparation should be performed in order to use the brazing filler as mentioned above as a target of sputtering. The preparation of the bulk target may use a powder metallurgy process, including preparing an alloy powder using a casting process by vacuum arc melting or gas atomizing and then bulking the alloy powder using some spark plasma sintering. A casting process allows giving a shape to a molten metal using a cast and then coagulating to prepare a crystalline structure.
Meanwhile, the powder metallurgy process allows preparing a desired shape through the processing, such as preparing a metal powder, then pressuring thereon, and the like, and then heating the desired shape at the temperature of not more than melting point of the metals therein to coagulate so that it is prepared as an amorphous state. Generally, the amolphous metal is used as a target of sputtering. However, there is an advantage that even though the target is the crystalline structure in the case of the filler according to the present invention, after sputtering it changes to the amorphous state, so that the filler can be prepared through the casting.
Hereinafter, the present invention will be described in more detail. However, the following Examples are only for illustrating the present invention, but the context is not limited to the following Examples.
<Example 1> Preparation of Zr62-Tin-Cu13-Ni14 Alloy Target Zr62-Ti11-Cu13-Ni14 alloy target was prepared by a casing process of 62 wt% of Zr, 11 wt% of Ti, 13 wt% of Cu, and 14 wt% of Ni using a vacuum arc melting furnace.
<Example 2> Brazing Joining 1 Using Zru-Ti 11-Cul3-Nim Filler Step 1. Introducing Filler to Joining Part through Sputter Coating A sputter coating was performed using the alloy prepared from Example 1 as a target after placing one side of Zircaloy-4 alloy to be used as a base metal of joining to the sputter apparatus. At this point, an initial high vacuum was set to be not more than 10-5 torr using a diffusion pump, a thin-film deposition pressure was set to be 2 x 10-2 torr, and an argon was supplied in 15 sccm to perform the coating for 120 minutes thereby introducing the filler prepared from Example 1 to the base metal of joining in a thickness of 70 F.
Step 2. Heating to Joining Part A infrared brazing was performed by preparing Zircaloy-4 alloy base metal to be joined to the side that was coated with the filler in Step 1. At this point, a rising temperature was W 100 C/min., and a maintenance temperature was 790 C when infrared heating. It was maintained at the above temperature for 10 minutes, then cooled in 50 C /min. for heating, and also was performed under the atmosphere of argon.
<Example 3> Brazing Joining 2 using Zr62-Tin-Cun-Ni Filler A brazing joining was performed with a base metal of joining by using the same process with Example 2, except that the maintenance temperature of Step 2 was 850 ct in Example 2.
<Example 4> Brazing Joining 3 using Zr72-Ti7-Cu8-Fe13Filler A brazing joining was performed with a base metal of joining by using the same process with Example 2, except that the maintenance temperature of Step 2 was 910 C in Example 2.
<Experimenting Example 1> XRD Analysis of Zr62-Ti11-Cu13-Ni14Filler Target In order to confirm a crystalline property of the filler target introduced to the sputter coating, the filler target prepared from Example 1 was analyzed using XRD (X-ray Diffraction) and then the results were shown in Fig. 2.
As shown in Fig. 2, it could be found that the target prepared by the vacuum arc melting has the crystalline W property, in which it crystals in various phases.
<Experimenting Example 2> XRD Analysis of Sputtered Zr62-Ti11-Cu13-Ni14 Filler Coating Layer In order to confilm the crystalline property of the filler-coating layer after sputtering, the Zr62-Ti _11-Cun-Nim filler coating layer obtained by performing only Step I of Example 2 was analyzed using XRD (X-ray Diffraction), and the results were shown in Fig. 3.
As shown in Fig. 3, it could be found that the structure of the filler alloy prepared from Example 1, in which the filler alloy was presented as the crystalline alloy, became an amorphous structure through sputtering. It means that even though the structure of target was crystalline, it can form an amorphous coating layer through sputtering.
<Experimenting Example 3> SEM Observation after Sputter Coating of Zr62-Ti11-Cu13-Ni1.4 Filler In order to confilm a uniformity of surface after coating of filler, a zirconium alloy specimen prepared by performing only Step 1 of Example 2 was observed through SEM, and then the results were shown in Fig. 4.
As shown in Fig. 4, it could be found that the filler was uniformly coated on the surface of base metals.
<Experimenting Example 4> Observation of Cross Section after Sputter Coating of Zru-Tin-Cun-NilAFiller In order to confirm as to whether the filler coated has a W unifoLm thickness, a cutting section of the sidepiece of the zirconium alloy specimen prepared by performing only Step 1 of Example 2 was observed using an optical microscope, and then the results were shown in Fig. 5.
As shown in Fig. 5, it could be found that the coating layer to the base metals was well coated with a uniform thickness and it formed a perfect interface.
<Experimenting Example 5> Heat Analysis after Sputter Coating of Zr62-Ti11-Cu13-Ni14 Filler In order to confiLm a liquidus temperature and solidus temperature of filler after sputter coating, the alloy prepared from Example 1 was sputter-coated on a vanadium thin-film under the same condition as disclosed in Step 1 of Example 2; then was heat-analyzed using DTA (Differential Thermal Analyzer); and then the results were shown in Fig. 6.
According to Fig. 6, a lateral axis indicates a In order to analysis a micro structure after brazing of filler joined from Example 3, it was observed using SEM and then the results were shown in Fig. 7.
Both sides of the joint were the structure of joining base metal. As shown in Fig. 7, it could be found that the brazing joining was properly performed because the joint has Zr containing solid solution phase that has not fragile intermetallic compounds due to the sufficient isothermal solidification diffusion between the filler and base metals.
<Experimenting Example 7> Observation of Micro structure after Brazing of Zr72-Ti7-Cu8-Fe13 Filler In order to analysis a micro structure after brazing of filler joined from Example 4, it was observed using SEM and then the results were shown in Fig. 8.
Both sides of the joint were the structure of joining base metal. As shown in Fig. 8, it could be found that the brazing joining was properly performed because the joint has Zr containing solid solution phase that has not fragile inteLmetallic compounds due to the sufficient isothermal solidification diffusion between the filler and base metals.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions, are possible.
The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.
Additionally, there is an advantage that a coating can be uniformly performed even on the parts with a wide area or complicated shapes so that it can be used for various parts as compared with ribbon-type or foil-type filler.
For Step 1, the joining base metal is a zirconium alloy, and in this situation, filler to be coated is preferably Zr-Ti-x-y or Zr-Ti-x-y-z (here, x, y, and z are one selected from the group consisting of alloy atoms including Cu, Ni, Fe, Al, M Sn, and Be, respectively, but x, y, and z are not identical).
The zirconium alloy is zirconium to which an element, such as, Sn, Fe, Cr, Ni, Cu, Nb, and the like, is added, and includes Zircaloy-1, Zircaloy-2, Zircaloy-3, Zircaloy-4, Low tin improved Zicaloy-4, Ozhennite, and the like. The zirconium alloy is an alloy that has very improved corrosion resistance and mechanical property as compared with a pure zirconium.
Since an alloy element is generally added in less than 2-3 %, a neutron absorption cross-sectional area of alloy is only very little increased in the degree of about 0.2 barn. The zirconium alloy is used for a nuclear fuel clad tube, guide tube, spacer grid, and the like of light-water reactor and heavy-water reactor due to the above features, and mainly used for a nuclear fuel clad tube, pressure tube, Calandria Tube, and the like.
The zirconium alloy is preferably Zircaloy-4. The general composition of Zircaloy-4 that is one type of the zirconium alloy includes 1.2-1.7 wt% of Sn, 0.18-0.24 wt% of Fe, 0.07-0.13 wt% of Cr, and a zirconium residue. The zirconium alloys that are developed for more improving a corrosion resistance and a mechanical property at the same time in cooling water under the conditions of high-temperature and high-pressure are used for a nuclear fuel clad tube of light-water reactor that is mainly used in the whole world power reactors until quite recently. There are Zircaloy-2, M Zircaloy-4, and Ozhennite that are used in the former Soviet Union as a typical alloy. Among those, Zircaloy-4 is frequently used for Pressurized Water Reactor (PWR).
The filler is preferably Zra-Tib-Cuc-Nid containing alloy (a, b, c, and d mean mass% of Zr, Ti, Cu, and Ni, respectively, and 305a570, 55b515, 85c520, and 105d520), and more preferably, has Zr62-Ti11-Cu13-Ni14 alloy composition, or Zra-Tib-Cuc-Fed containing alloy (a, b, c, and d mean mass% of Zr, Ti, Cu, and Fe, respectively, and 405a580, 55b515, 55c515, and 55d515), and more preferably, has Zr72-Ti7-Cu8-Fe13 alloy composition. Since the alloy has low melting point, it has an effect in preventing erosion, a modification, and a mechanical deterioration of base metals when heat-treating for brazing.
The thickness of the filler to be coated in Step 1 is preferably 5-200 gm. There are limitations that when the thickness of the filler is below 5 M, it is not sufficient for a role as a joining material, and when the thickness of the filler exceeds 200 M, an excessive amount of filler flows out in a liquid phase when melting or a good joint structure is difficult to form.
Step 2 according to the present invention to heat to a joining part. With reference to the mimetic diagram as shown in Fig. 1, the principle of the brazing according to the W present invention is as follows. When solid filler(B) is added between the base metals(Al, A2), and then heated, the filler is melted and then liquid filler and base metals are diffused so that the joining between the filler and base metals is done due to isothermal solidification diffusion.
Meanwhile, infrared heating equipment among heat transfer equipments is known as very fast heat transfer equipment because most atomic bonds of objects are easily excitated in an infrared radiation area due to an electro-magnetic radiation. Additionally, an infrared heating has an advantage that it can heat only desired part by a direct radiation thereto using a coldwall process. Accordingly, the infrared heating with the above-explained advantages may be efficiently used for the heating of Step 2, but not limited thereto.
For Step 2, when the joining base metals is a zirconium alloy and the filler to be coated is Zra-Tib-Cuc-Nid (a, b, c, and d are mass% of Zr, Ti, Cu, and Ni, respectively, and 305a570, 55b15, 85.c20, and 10,0120), preferably the maintenance temperature is 720 - 1050 C and the maintenance period is 0.5 - 60 minutes. Since the ranges of solidus temperature and liquidus temperature of Zra-Tib-Cuc-Nid (a, b, c, and d are mass% of Zr, Ti, Cu, and Ni, respectively, and 305a570, 85-c520, and 105d520) alloy are 720 - 1050 C, to there are limitations that when the maintenance temperature is below 720 "ID, the filler is not melted so that the brazing is not performed and when the maintenance temperature exceeds 1050 C, a fine structure modification or excessive erosion is caused to the base metals.
Moreover, the maintenance temperature is more preferably minimum at least 30 ct than the melting temperature of filler when heating.
For Step 2, when the joining base metals is a zirconium alloy and the filler to be coated is zra-Tib-Cuc-Fed (a, b, c, and d are mass% of Zr, Ti, Cu, and Fe, respectively, and 405a80, 55c515, and 5c1.15), preferably the maintenance temperature is 720 - 1050 cC and the maintenance period is 0.5 - 60 minutes. Since the ranges of solidus temperature and liquidus temperature of Zra-Tib-Cuc-Fed (a, b, c, and d are mass% of Zr, Ti, Cu, and Fe, respectively, and 405a580, 551D15, 5c515, and 5ci-5_15) alloy are 720 - 1050 C, there are limitations that when the maintenance temperature is below 720 C, the filler is not melted so that the brazing is not performed and when the maintenance temperature exceeds 1050 C, a fine structure modification or excessive erosion is caused to the base metals.
Moreover, the maintenance M temperature is more preferably minimum at least 30 C than the melting temperature of filler when heating.
For Step 2, the heat treating is preferably performed under an inert atmosphere, such as, for example an argon atmosphere. There is an effect on preventing the production of impurities of alloy in the joining material by blocking the contact with oxygen during heat-treating.
The brazing method for joining according to the present invention may be usefully applied to a nuclear fuel rod of heavy-water reactor. For the brazing of nuclear fuel rod of the conventional heavy-water reactor, a beryllium is deposited and then heat is applied to join, but there was limitation that a flaking phenomenon, in which a beryllium layer is fallen out during the brazing process, is generated to cause the defect of the joint, in addition to a harmful problem of beryllium. For another method, Zr-Be alloy was prepared to use for brazing, but there was limitation that the operation should be performed at high temperature of above 1050 'C and the structural safety of the joint is not secured. Meanwhile, for the brazing method for joining using the sputter coating layer according to the present invention as a filler, there are advantages that when coating on the surface of base metals using the sputtering method that is one of physical vapor W depositions, the multi-component target composition can be intactly maintained on the coating layer of the surface of base metals; the thickness can be easily controlled; it can be uniformly applied to the surface of base metals; and also the perfect contact can be maintained on the interface.
Therefore, the unifoLmity and reproducibility of the joint can be secured.
Additionally, the present invention provides amorphous brazing filler used for the method for joining, in which the filler is Zr-Ti-x-y or Zr-Ti-x-y-z (here, x, y, and z are one selected from the group consisting of alloy elements including Cu, Ni, Fe, Al, Sn, and Be, respectively, but x, y, and z are not identical). When the alloy elements, such as, Cu, Ni, Fe, Al, Sn, and Be, are added to the zirconium alloy, the melting point of the inserting alloy is decreased so that the temperature for joining can be decreased and also the joint with the same corrosion resistance and mechanical property as the zirconium alloy that is base metals can be secured by maximizing the joint structure.
The brazing filler can be usefully applied to the zirconium alloy joining. The zirconium that consists the brazing filler has a thermal neutron absorption cross-section of 0.18 barn that is smaller than 0.23 barn of aluminum as well as about 3.2 barn of stainless steel. Moreover, it is M very suitable to use as a reactor core material of a nuclear reactor because it has excellent mechanical property and corrosion resistance and also excellent compatability with uranium dioxide (UO2) that is used as a nuclear fuel.
The filler preferably includes 30-70 wt% of Zr, 5-15 wt%
of Ti, 8-20 wt% of Cu, and 10-20 wt% of Ni, and the contents of the filler are more preferably 62 wt% of Zr, 11 wt% of Ti, 11 wt% of Cu, and 14 wt% of Ni, respectively. The melting and coagulation phenomenon are occurred in the very narrow range of temperature for the brazing filler.
Specifically, the ranges of liquidus temperature and solidus temperature of the filler that is Zr30_70-Tis-15-Cue-20-Ni10-20 according to the present invention are 720 - 950 C, and the solidus temperature is 770 00 and the liquidus temperature is 815 C in the case of the brazing filler with Zr62-Ti11-Cu13-Ni14 alloy composition.
Also, The filler preferably includes 40-80 wt% of Zr, 5-15 wt%
of Ti, 5-15 wt % of Cu, and 5-15 wt% of Fe, and the contents of the filler are more preferably 72 wt% of Zr, 7 wt% of Ti, 8 wt% of Cu, and 13 wt% of Fe, respectively. The melting and coagulation phenomenon are occurred in the very narrow range of temperature for the brazing filler.
Specifically, the ranges of liquidus temperature and solidus temperature of the filler that is Zr40-80-Ti5_15-Cu5....15-Fe5_15 according to the present invention are 720 - 1050 00, and the solidus temperature is 820 "ID and the liquidus temperature is 845 C in the case of the brazing filler with Zr72-T17-Cu8-Fe13 alloy composition. As mentioned above, there are advantages that the brazing filler has a narrow melting temperature range, so that the ununiformly melting of the filler is reduced thereby improving a flow rate and the brazing filler has a low melting temperature so that the structural modification and the decrease of the mechanical property of base metals are not caused, and also it is possible to join.
The brazing filler with Zr62-Ti11-Cu13-Ni14 alloy composition according to the present invention has low melting point as mentioned above, and it can be explained from the fact of the eutectic reaction between the component phases that consists the composition. When the content of nickel is constant as 33.3 atom% for the alloy system consisting of Zr-Ti-Ni, the component phase of zirconium-rich area is consisted of two phases of Zr2Ni and (Zr, Ti)2Ni phases and it is known that there is Zr2Ni-(Zr, Ti)2Ni binary eutectic point of 850 'C
by the eutectic reaction between the component phases, and in this situation, copper is added as a melting point depprassant to obtain more low-melting point. That is, Zr-Ti-Cu-Ni quarternary alloy composition allows to more reducing the solidus temperature and liquidus temperature by substituting a part of nickel that is included in Zr-Ti-Ni ternary alloy M composition with copper.
Therefore, there is an advantage that the structural modification and deterioration damage of base metals can be minimized by using the alloy composition as mentioned above as the brazing filler.
A bulk target preparation should be performed in order to use the brazing filler as mentioned above as a target of sputtering. The preparation of the bulk target may use a powder metallurgy process, including preparing an alloy powder using a casting process by vacuum arc melting or gas atomizing and then bulking the alloy powder using some spark plasma sintering. A casting process allows giving a shape to a molten metal using a cast and then coagulating to prepare a crystalline structure.
Meanwhile, the powder metallurgy process allows preparing a desired shape through the processing, such as preparing a metal powder, then pressuring thereon, and the like, and then heating the desired shape at the temperature of not more than melting point of the metals therein to coagulate so that it is prepared as an amorphous state. Generally, the amolphous metal is used as a target of sputtering. However, there is an advantage that even though the target is the crystalline structure in the case of the filler according to the present invention, after sputtering it changes to the amorphous state, so that the filler can be prepared through the casting.
Hereinafter, the present invention will be described in more detail. However, the following Examples are only for illustrating the present invention, but the context is not limited to the following Examples.
<Example 1> Preparation of Zr62-Tin-Cu13-Ni14 Alloy Target Zr62-Ti11-Cu13-Ni14 alloy target was prepared by a casing process of 62 wt% of Zr, 11 wt% of Ti, 13 wt% of Cu, and 14 wt% of Ni using a vacuum arc melting furnace.
<Example 2> Brazing Joining 1 Using Zru-Ti 11-Cul3-Nim Filler Step 1. Introducing Filler to Joining Part through Sputter Coating A sputter coating was performed using the alloy prepared from Example 1 as a target after placing one side of Zircaloy-4 alloy to be used as a base metal of joining to the sputter apparatus. At this point, an initial high vacuum was set to be not more than 10-5 torr using a diffusion pump, a thin-film deposition pressure was set to be 2 x 10-2 torr, and an argon was supplied in 15 sccm to perform the coating for 120 minutes thereby introducing the filler prepared from Example 1 to the base metal of joining in a thickness of 70 F.
Step 2. Heating to Joining Part A infrared brazing was performed by preparing Zircaloy-4 alloy base metal to be joined to the side that was coated with the filler in Step 1. At this point, a rising temperature was W 100 C/min., and a maintenance temperature was 790 C when infrared heating. It was maintained at the above temperature for 10 minutes, then cooled in 50 C /min. for heating, and also was performed under the atmosphere of argon.
<Example 3> Brazing Joining 2 using Zr62-Tin-Cun-Ni Filler A brazing joining was performed with a base metal of joining by using the same process with Example 2, except that the maintenance temperature of Step 2 was 850 ct in Example 2.
<Example 4> Brazing Joining 3 using Zr72-Ti7-Cu8-Fe13Filler A brazing joining was performed with a base metal of joining by using the same process with Example 2, except that the maintenance temperature of Step 2 was 910 C in Example 2.
<Experimenting Example 1> XRD Analysis of Zr62-Ti11-Cu13-Ni14Filler Target In order to confirm a crystalline property of the filler target introduced to the sputter coating, the filler target prepared from Example 1 was analyzed using XRD (X-ray Diffraction) and then the results were shown in Fig. 2.
As shown in Fig. 2, it could be found that the target prepared by the vacuum arc melting has the crystalline W property, in which it crystals in various phases.
<Experimenting Example 2> XRD Analysis of Sputtered Zr62-Ti11-Cu13-Ni14 Filler Coating Layer In order to confilm the crystalline property of the filler-coating layer after sputtering, the Zr62-Ti _11-Cun-Nim filler coating layer obtained by performing only Step I of Example 2 was analyzed using XRD (X-ray Diffraction), and the results were shown in Fig. 3.
As shown in Fig. 3, it could be found that the structure of the filler alloy prepared from Example 1, in which the filler alloy was presented as the crystalline alloy, became an amorphous structure through sputtering. It means that even though the structure of target was crystalline, it can form an amorphous coating layer through sputtering.
<Experimenting Example 3> SEM Observation after Sputter Coating of Zr62-Ti11-Cu13-Ni1.4 Filler In order to confilm a uniformity of surface after coating of filler, a zirconium alloy specimen prepared by performing only Step 1 of Example 2 was observed through SEM, and then the results were shown in Fig. 4.
As shown in Fig. 4, it could be found that the filler was uniformly coated on the surface of base metals.
<Experimenting Example 4> Observation of Cross Section after Sputter Coating of Zru-Tin-Cun-NilAFiller In order to confirm as to whether the filler coated has a W unifoLm thickness, a cutting section of the sidepiece of the zirconium alloy specimen prepared by performing only Step 1 of Example 2 was observed using an optical microscope, and then the results were shown in Fig. 5.
As shown in Fig. 5, it could be found that the coating layer to the base metals was well coated with a uniform thickness and it formed a perfect interface.
<Experimenting Example 5> Heat Analysis after Sputter Coating of Zr62-Ti11-Cu13-Ni14 Filler In order to confiLm a liquidus temperature and solidus temperature of filler after sputter coating, the alloy prepared from Example 1 was sputter-coated on a vanadium thin-film under the same condition as disclosed in Step 1 of Example 2; then was heat-analyzed using DTA (Differential Thermal Analyzer); and then the results were shown in Fig. 6.
According to Fig. 6, a lateral axis indicates a In order to analysis a micro structure after brazing of filler joined from Example 3, it was observed using SEM and then the results were shown in Fig. 7.
Both sides of the joint were the structure of joining base metal. As shown in Fig. 7, it could be found that the brazing joining was properly performed because the joint has Zr containing solid solution phase that has not fragile intermetallic compounds due to the sufficient isothermal solidification diffusion between the filler and base metals.
<Experimenting Example 7> Observation of Micro structure after Brazing of Zr72-Ti7-Cu8-Fe13 Filler In order to analysis a micro structure after brazing of filler joined from Example 4, it was observed using SEM and then the results were shown in Fig. 8.
Both sides of the joint were the structure of joining base metal. As shown in Fig. 8, it could be found that the brazing joining was properly performed because the joint has Zr containing solid solution phase that has not fragile inteLmetallic compounds due to the sufficient isothermal solidification diffusion between the filler and base metals.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions, are possible.
The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.
Claims (6)
1. A brazing method for joining using an amorphous sputtered coating layer as a filler, the brazing method comprising:
forming an amorphous coating layer through a sputter coating on a joining part between base metals (Step 1); and heating the joining part of Step 1 (Step 2), wherein the each of said base metal is a zirconium alloy, wherein the filler is Zr a-Ti b-Cu c-Ni d containing alloy where a, b, c, and d mean mass% of Zr, Ti, Cu, and Ni, respectively, and 30<=a<=70, 5<=b<=15, 8<=c<=20, and 10<=d<=20.
forming an amorphous coating layer through a sputter coating on a joining part between base metals (Step 1); and heating the joining part of Step 1 (Step 2), wherein the each of said base metal is a zirconium alloy, wherein the filler is Zr a-Ti b-Cu c-Ni d containing alloy where a, b, c, and d mean mass% of Zr, Ti, Cu, and Ni, respectively, and 30<=a<=70, 5<=b<=15, 8<=c<=20, and 10<=d<=20.
2. The brazing method as set forth in claim 1, wherein the thickness of the filler to be coated in Step 1 is 5 µm to 200 µm.
3. The brazing method as set forth in claim 1, wherein the heating of Step 2 is performed at a maintenance temperature of 720°C to 1050°C.
4. The brazing method as set forth in claim 1, wherein the brazing method is used for a nuclear fuel rod of a heavy-water reactor.
5. An amorphous brazing filler used for a brazing method as set forth in claim 1, wherein the filler is Zr a-Ti b-Cu c-Ni d filler containing alloy where a, b, c, and d mean mass% of Zr, Ti, Cu, and Ni, respectively, and 30<=a<=70, 5<=b<=15, 8<=c<=20, and 10<=d<=20.
6. The amorphous brazing filler as set forth in claim 5, wherein the solidus temperature and liquidus temperature of the brazing filler range from 720°C to 1050°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2011-0000848 | 2011-01-05 | ||
| KR1020110000848A KR20120079587A (en) | 2011-01-05 | 2011-01-05 | The brazing method of joining using amorphous sputtered coating layer as a filler and the amorphous brazing filler used for it |
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| CA2763153C true CA2763153C (en) | 2016-04-12 |
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| KR101446713B1 (en) * | 2013-04-19 | 2014-10-06 | 한국원자력연구원 | Zirconium based alloy compositions for brazing filler to obtain improved corrosion resistance in zirconium or zirconium based alloy joints and joining method using the same |
| KR101466039B1 (en) * | 2013-06-11 | 2014-11-27 | 한국생산기술연구원 | Method of bonding crystalline alloys including metal element having glass forming ability, target structure for sputtering and method of fabricating the same |
| KR20160050663A (en) * | 2014-10-30 | 2016-05-11 | 한국생산기술연구원 | Method of fabricating nano structured film including nitrogen and amorphous film |
| CN104962796B (en) * | 2015-06-30 | 2019-03-01 | 深圳迈辽技术转移中心有限公司 | A kind of medical zirtan and preparation method thereof |
| US10450643B2 (en) | 2016-07-13 | 2019-10-22 | Hamilton Sundstrand Corporation | Material joining |
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| CA2763153A1 (en) | 2012-07-05 |
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