JPS5948959B2 - Internal electroplating method for zirconium alloy tubes - Google Patents
Internal electroplating method for zirconium alloy tubesInfo
- Publication number
- JPS5948959B2 JPS5948959B2 JP53118273A JP11827378A JPS5948959B2 JP S5948959 B2 JPS5948959 B2 JP S5948959B2 JP 53118273 A JP53118273 A JP 53118273A JP 11827378 A JP11827378 A JP 11827378A JP S5948959 B2 JPS5948959 B2 JP S5948959B2
- Authority
- JP
- Japan
- Prior art keywords
- zirconium alloy
- alloy tube
- plating
- tube
- zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910001093 Zr alloy Inorganic materials 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 22
- 238000009713 electroplating Methods 0.000 title claims description 11
- 238000007747 plating Methods 0.000 claims description 25
- 238000005554 pickling Methods 0.000 claims description 14
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000003758 nuclear fuel Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005253 cladding Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
本発明は、例えば原子燃料用被覆管として使用できるジ
ルコニウム合金管の内面電気メッキ法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for electroplating the inner surface of a zirconium alloy tube that can be used, for example, as a cladding tube for nuclear fuel.
原子燃料用被覆管としては、燃料棒を完全に密閉保護で
きる金属鋼体保護管が用いられ、これを被覆した核燃料
棒は、原子炉内において目的とした出力と理想的な熱均
等性が得られるように組立てられる。Metallic steel protection tubes are used as nuclear fuel cladding tubes to completely seal and protect the fuel rods. Nuclear fuel rods coated with this tube can achieve the desired output and ideal thermal uniformity inside the reactor. It is assembled so that it can be used.
また、かかる被覆管には耐熱性、非反応性、非腐食性、
機械的強靭性が要求され、現在アルミニウム合金、ステ
ンレス鋼、ジルコニウム合金（ジルカロイ）が用いられ
ている。In addition, such cladding is heat resistant, non-reactive, non-corrosive,
Mechanical toughness is required, and currently aluminum alloys, stainless steel, and zirconium alloys (Zircaloy) are used.
このうち特にジルコニウム合金からなる管は、６００℃
以下の温度では強度が大きく、中性子吸収断面積がステ
ンレスより小さく高価ではあるが、低濃縮ウラン燃料を
使用できるために軽水冷却動力炉ではほとんどこのジル
コニウム合金管が使用されている。Among these, tubes made of zirconium alloy in particular are heated to 600°C.
Zirconium alloy tubes are strong at temperatures below, have a smaller neutron absorption cross section than stainless steel, and are more expensive, but because they can use low-enriched uranium fuel, zirconium alloy tubes are mostly used in light water-cooled power reactors.
ジルコニウム合金にはその組成によつてジルカロイ１か
らジルカロイ４まで種類があり、夫々組成を示すと次表
の通りである。There are different types of zirconium alloys, from Zircaloy 1 to Zircaloy 4, depending on their composition, and the compositions of each are shown in the table below.
表−１ジルカロイの組成
″ ジルカロイ２は錫を減じ耐食性を高めたもので、ジ
ルカロイ３はさらに錫を減じ加工性を高めたものである
。Table 1: Composition of Zircaloy Zircaloy 2 has a reduced tin content to improve corrosion resistance, and Zircaloy 3 has a further reduced tin content to improve workability.
またジルカロイ４は水素吸収脆化を改良するためにニッ
ケルを除いて鉄を増した脆化防止改良型合金である。し
かし、このように改良を加えられたジルコニウム合金に
も、炉心の安全上重大な欠陥のあることが明らかとなつ
た。Zircaloy 4 is an improved anti-embrittlement alloy that removes nickel and increases iron to improve hydrogen absorption embrittlement. However, it has become clear that even this improved zirconium alloy has serious defects in terms of core safety.
それは、
（１）核分裂反応の際に生じた核分裂生成物との間の相
互作用によつて、ジルコニウム合金管内面に脆い層が形
成するということである。(1) A brittle layer is formed on the inner surface of the zirconium alloy tube due to interaction with fission products generated during the nuclear fission reaction.
この脆い層は、ジルコニウム合金管とＵＯ２ペレツトな
どの原子燃料との熱膨張率の相違により、高温ではペレ
ツトが膨張してジルコニウム合金管に拡張応力が加わり
、応力腐食割れを生じる危険を有している。This brittle layer is caused by the difference in coefficient of thermal expansion between the zirconium alloy tube and nuclear fuel such as UO2 pellets, which causes the pellet to expand at high temperatures, applying expansion stress to the zirconium alloy tube, which poses the risk of stress corrosion cracking. There is.
（２）ジルコニウム合金管が上記ＵＯ２と直接に反応し
てＺＩＯ２を形成し、すなわち燃料と焼結するという問
題を生じる。(2) A problem arises in that the zirconium alloy tube reacts directly with the UO2 to form ZIO2, that is, it sinters with the fuel.
（３）ジルカロイ管内部の残存水分が密閉された条件下
で水素ガスとなり、ジルカロイ管に局部的な水素脆化を
もたらす危険があること等である。(3) There is a risk that residual moisture inside the Zircaloy tube becomes hydrogen gas under sealed conditions, causing local hydrogen embrittlement of the Zircaloy tube.
この安全上重大な障害を防止するために考えられた種々
の方法のうち、最近ジルコニウム合金管の内面に銅、ニ
ツケル等の障壁層を設けることが決定的な効果をもつこ
とが、種々の応力腐食試験や脆化試験、被覆燃料棒出力
試験により明らかとなつた。Among the various methods that have been devised to prevent this serious safety problem, it has recently been found that providing a barrier layer of copper, nickel, etc. on the inner surface of the zirconium alloy tube has a decisive effect on preventing various stresses. This was revealed through corrosion tests, embrittlement tests, and coated fuel rod output tests.
具体的には特開昭５１−６９７９２、特開昭５１一６９
７９３、特開昭５３−６２７４０に示されているように
、銅、ニツケル、鉄あるいはこれらの合金層を施す方法
、及びクロムの拡散障壁層を施した上に銅、ニツケル、
鉄の金属層を施す方法が提案されている。Specifically, JP-A-51-69792, JP-A-51-69
793, JP-A No. 53-62740, there is a method of applying a layer of copper, nickel, iron or an alloy thereof, and a method of applying a layer of copper, nickel, iron or an alloy of these on a chromium diffusion barrier layer.
A method of applying a metal layer of iron has been proposed.
特に、酸洗液の使用に際して、二度熟成という不明確な
作業を行なつており、管理が不可能である。In particular, when using a pickling solution, an unclear process of double aging is performed, which is impossible to control.
しかしながら、上記特許は原理的には実証試験により裏
付けられた方法であり、その効果は疑う余地のないとこ
ろであるが、実際にこれら金属層をジルコニウム合金管
の内面に施す方法については完全な方法を提示していな
い。However, although the above patent is a method that has been backed up by demonstration tests in principle, and its effectiveness is beyond doubt, there is no complete method for actually applying these metal layers to the inner surface of the zirconium alloy tube. Not presented.
本発明を提案する理由はこの点にあり、それはジルコニ
ウム合金管の内面に電気メツキによりニツケル、銅等の
金属を密着性良く施すことがきわめて難しいということ
に基いている。This is the reason for proposing the present invention, and is based on the fact that it is extremely difficult to apply metals such as nickel or copper with good adhesion to the inner surface of a zirconium alloy tube by electroplating.
我々は過去の実験知識、及びこれについて現在まで行な
つた実験データにより、上記特許は理論的には正しいが
、実際に障壁層を形成させる手法については未完成であ
ることを確認した。Based on our past experimental knowledge and the experimental data we have conducted to date, we have confirmed that although the above patent is theoretically correct, the method for actually forming a barrier layer is incomplete.
したがつて本発明は、原子燃料用被覆管として使用でき
るジルコニウム合金管の内面に電気メツキにより銅、ニ
ツケル、鉄などの金属層を密着性良く形成できる方法を
提供することを目的とするものである。Therefore, an object of the present invention is to provide a method for forming a metal layer of copper, nickel, iron, etc. with good adhesion by electroplating on the inner surface of a zirconium alloy tube that can be used as a cladding tube for nuclear fuel. be.
本発明は、原子燃料用被覆管としてのジルコニウム合金
管に限定されるものではないが、そのような用途に使用
した場合には、重大なる原子炉の安全を確保するという
点で、極めて多大な効果をもたらすものである。Although the present invention is not limited to zirconium alloy tubes as cladding tubes for nuclear fuel, when used in such applications, it has an extremely large effect on ensuring the safety of nuclear reactors. It is something that brings about an effect.
本発明の要旨は、ジルコニウム合金管の内面に金属を電
気メツキするに際して、メツキの前処理である酸洗活性
化処理を、フツ化アンモン０．２〜１．５モル、フツ酸
０．０５〜０．５モルの組成の、モル比がＮＨ４／ＨＦ
＝１．２〜１５の酸洗液で行ない、その後合金管の内面
を超音波洗浄処理し、メツキの際は合金管の中をメツキ
液を循環させながらメツキを行なうことを特徴とするジ
ルコニウム合金管の内面電気メツキ法にある。The gist of the present invention is that when electroplating metal on the inner surface of a zirconium alloy tube, a pickling activation treatment, which is a pretreatment for plating, is performed using 0.2 to 1.5 mol of ammonium fluoride and 0.05 to 0.05 mol of fluoric acid. With a composition of 0.5 mol, the molar ratio is NH4/HF
= 1.2 to 15, and then the inner surface of the alloy tube is subjected to ultrasonic cleaning treatment, and during plating, the plating is performed while circulating the plating liquid inside the alloy tube. This method is for electroplating the inner surface of pipes.
なお、上記ジルコニウム合金管には、ジルコニウム管も
含まれるものである。Note that the above-mentioned zirconium alloy tube also includes a zirconium tube.
すなわち、この種金属管においては、ジルコニウムを主
体とした合金管が普通使用されるので、本発明ではその
ように名称したものである。酸洗活性化処理に使用され
る酸洗液の組成は、例えば下記の通りであり、Ｈ２Ｏは
これに限定されない。That is, in this type of metal tube, since an alloy tube mainly composed of zirconium is commonly used, it is named as such in the present invention. The composition of the pickling solution used in the pickling activation treatment is, for example, as follows, and H2O is not limited thereto.
上記組成の酸洗液は、管理範囲が広く作業が容易であり
、実験によりジルコニウム合金に対して有効なものと認
められたものである。The pickling solution having the above composition has a wide control range, is easy to work with, and has been found to be effective for zirconium alloys through experiments.
しかし、この酸洗液でジルコニウム合金を活性化処理し
た場合、表面に不溶解性の残渣が生じる。However, when a zirconium alloy is activated with this pickling solution, an insoluble residue is produced on the surface.
本発明では、この残渣を除去する方法として、酸洗活性
化処理後のジルコニウム合金管の内面を超音波洗浄処理
するものである。In the present invention, as a method for removing this residue, the inner surface of the zirconium alloy tube after the pickling activation treatment is subjected to an ultrasonic cleaning treatment.
超音波洗浄処理は、普通水中にジルコニウム合金管を浸
漬させて行なえば良く、その際水を循環させればより効
果的である。超音波照射時間は、超音波の出力や付加方
法によつて変るが、後述する実施例を基準に考えれば、
２９ＫＨｚ、６００Ｗで、３０秒程度で十分である。The ultrasonic cleaning treatment can be carried out by immersing the zirconium alloy tube in normal water, and it is more effective if the water is circulated. The ultrasonic irradiation time varies depending on the ultrasonic output and the application method, but based on the examples described below,
At 29KHz and 600W, about 30 seconds is sufficient.
超音波処理の際、さらに管内に通水をしないで行なうこ
とも可能であるが、残渣をより完全に除去するためには
、通水をして行なう方法が最適で．ある。次に添付図面
を参照して本発明ジルコニウム合金管の内面電気メツキ
法の実施例を説明する。Although it is possible to perform the ultrasonic treatment without passing water through the pipe, in order to remove the residue more completely, it is best to perform the ultrasonic treatment with water passing through the pipe. be. Next, an embodiment of the method for electroplating the inner surface of a zirconium alloy tube according to the present invention will be described with reference to the accompanying drawings.
第１図は、電気メツキ状況を示すものであり、］は内面
を電気メツキすべき長さ４ｍ、内径１０．８ノＭｍφ、
肉厚０．８６ｍｍｔのジルカロイ２からなるジルコニウ
ム合金管である。２はこのジルコニウム合金管１の中心
に挿通配置された陽極棒、３，３はプラスチツク製の端
末治具、４はメツキ液、５は循環ポンプ、６は配管、７
は陰極である。Figure 1 shows the electroplating situation, where ] indicates the length to be electroplated on the inner surface, 4 m, the inner diameter of 10.8 mmφ,
This is a zirconium alloy tube made of Zircaloy 2 with a wall thickness of 0.86 mm. 2 is an anode rod inserted through the center of this zirconium alloy tube 1, 3, 3 is a plastic terminal jig, 4 is a plating liquid, 5 is a circulation pump, 6 is piping, 7
is the cathode.
また、第２図は超音波処理状況を示すものであり、洗浄
水８を満たした超音彼処理槽９内に、ジルコニウム合金
管１と超音波振動子１０を入れ、超音波振動子１０はモ
ーター１１によつて左右に移動させ、合金管１の一端に
は通水管１２を連結、してなる。FIG. 2 shows the state of ultrasonic treatment, in which a zirconium alloy tube 1 and an ultrasonic vibrator 10 are placed in an ultrasonic treatment tank 9 filled with cleaning water 8, and the ultrasonic vibrator 10 is It is moved left and right by a motor 11, and a water pipe 12 is connected to one end of the alloy pipe 1.
実施例 １
第１図及び第２図に示される装置及びジルコニウム合金
管を用いて、下記処理工程で銅メツキを行なつた。Example 1 Using the apparatus shown in FIGS. 1 and 2 and a zirconium alloy tube, copper plating was carried out in the following processing steps.
（１）脱脂 アルカリ洗浄脱脂を行なつた。(1) Degreasing Alkaline cleaning and degreasing were performed.
（２）水洗
（３）酸洗活性化処理
ＮＨ４ＦＯ．２モル／１、ＨＦＯ．ｌモル／ｌの水溶液
からなる酸洗液をジルコニウム合金管内に５分間充填し
て行なつた。(2) Water washing (3) Pickling activation treatment NH4FO. 2 mol/1, HFO. A pickling solution consisting of an aqueous solution of 1 mol/l was filled into a zirconium alloy tube for 5 minutes.
（４）超音波洗浄処理
第２図において、ジルコニウム合金管１内を通水し、か
つ超音波振動子１０によつて、１分間における単位長さ
当り出力６００Ｗ、外部照射２９ＫＨｚの超音波付加を
行なつた。(4) Ultrasonic cleaning process In FIG. 2, water is passed through the zirconium alloy tube 1, and ultrasonic waves are applied using an ultrasonic vibrator 10 at an output of 600 W per unit length for 1 minute and an external irradiation frequency of 29 KHz. I did it.
（５）水洗
（６）銅メツキ
シアン化銅６０ｇ／１．シアン化ナトリウム７５ｇ／１
．シアン化カリウム１０ｇハからなるシアン化銅メツキ
浴を循環させて用いて、電流密度１Ａ／Ｄｍ２で、１０
μ厚の銅メツキを行なつた。(5) Washing with water (6) Copper methoxyanide 60g/1. Sodium cyanide 75g/1
．． Using a circulating copper cyanide plating bath consisting of 10 g of potassium cyanide, at a current density of 1 A/Dm2, 10
Copper plating with a thickness of μ was performed.
（７）水洗、乾燥この方法により製作した、内面銅メツ
キ被覆ジルコニウム合金管のメツキ密着性を調べるため
、その管を３００℃の真空炉に３時間入れて加熱試験を
行なつた。(7) Water washing and drying In order to examine the plating adhesion of the inner copper-plated zirconium alloy tube manufactured by this method, the tube was placed in a vacuum oven at 300° C. for 3 hours to perform a heating test.
同時に、超音波洗浄処理を行なわないで製作した内面銅
メツキ被覆ジルコニウム合金管についても加熱試験を行
なつた。At the same time, a heating test was also conducted on a zirconium alloy tube coated with copper plating on the inner surface, which was manufactured without ultrasonic cleaning treatment.
この結果、超音波洗浄処理を行なつた合金管には、試験
後メツキ層のフクレが認められなかつたのに対し、超音
波洗浄処理を行なわなかつた合金管には、メツキ進行時
にすでにフクレが発生していたものが、加熱試験により
さらに部分的な剥離となつて認められた。As a result, no blisters were observed in the plating layer of the alloy tubes that had been subjected to ultrasonic cleaning treatment after the test, whereas blisters were already observed in the alloy tubes that had not been ultrasonically cleaned during the plating process. What had occurred was further observed to be partially peeled off in a heating test.
超音波洗浄処理を行なつたものは、４５０℃の真空加熱
試験でも、密着性は良好であつた。実施例 ２
実施例１と同様に、ジルコニウム合金管の内面にニツケ
ルメツキを施し、内面ニツケルメツキ被覆ジルコニウム
合金管を製作した。Those subjected to ultrasonic cleaning showed good adhesion even in a vacuum heating test at 450°C. Example 2 In the same manner as in Example 1, nickel plating was applied to the inner surface of a zirconium alloy tube to produce a zirconium alloy tube whose inner surface was coated with nickel plating.
処理工程は、実施例１と同様であるが、酸洗活性化処理
は、ＮＨ４ＦＯ．６モル／１．ＨＦＯ．２モル／１の水
溶液からなる酸洗液を用い、ニツケルメツキは、ワツト
浴でＰｆｌ４．５、３Ａ／Ｄｍ２で１０μ厚にメツキし
た。The treatment steps are the same as in Example 1, but the pickling activation treatment is performed using NH4FO. 6 mol/1. HFO. Using a pickling solution consisting of a 2 mol/1 aqueous solution, nickel plating was performed in a Watt bath with a Pfl of 4.5 and a thickness of 3 A/Dm2 to a thickness of 10 μm.
上記方法により製作した、内面ニツケルメツキ被覆ジル
コニウム合金管を、実施例１と同様に真空加熱した結果
、超音波洗浄処理を行なわなかつたものは、フクレが発
生したが、超音波洗浄処理を行なつたものは、何ら異常
は認められなかつた。As a result of vacuum heating the zirconium alloy tube coated with nickel plating on the inner surface produced by the above method in the same manner as in Example 1, the tube without the ultrasonic cleaning treatment had blisters, but the tube with the ultrasonic cleaning treatment did not. No abnormalities were observed.
超音波洗浄処理したものは、４５０℃の真空加熱試験で
も、密着性は良好であつた。The ultrasonic cleaning treatment showed good adhesion even in a vacuum heating test at 450°C.
また、実施例１、実施例２では、製品の断面を光学顕微
鏡で観察した結果、メツキ層とジルコニウム合金の界面
には、スマツトの付着が認められず、均一な電気メツキ
結晶の成長が確認された。In addition, in Examples 1 and 2, as a result of observing the cross section of the product with an optical microscope, no adhesion of smut was observed at the interface between the plating layer and the zirconium alloy, and uniform electroplated crystal growth was confirmed. Ta.
以上のように、本発明ジルコニウム合金管の内面電気メ
ツキ法によれば、特定の酸洗液を用いた酸洗活性化処理
と超音彼洗浄処理を行なうことによつて、電気メツキに
よりきわめて密着性の優れたメツキ層を得ることがで゛
き、それによつて品質的に優れた製品を得ることができ
る。このため、本発明を原子燃料被覆用ジルコニウム合
金管の製造に適用した場合、得られた製品は原子炉の安
全確保にきわめて多大な効果をもたらすことができる。As described above, according to the method of electroplating the inner surface of a zirconium alloy tube according to the present invention, by performing pickling activation treatment using a specific pickling solution and ultrasonic cleaning treatment, extremely close adhesion can be achieved by electroplating. A plating layer with excellent properties can be obtained, and thereby a product with excellent quality can be obtained. Therefore, when the present invention is applied to the production of zirconium alloy tubes for cladding nuclear fuel, the resulting product can have an extremely large effect on ensuring the safety of nuclear reactors.
第１図は本発明に係るメツキ状況を示す説明図、第２図
は同本発明に係る超音波洗浄処理状況を示す説明図であ
る。
１：ジルコニウム合金管、２：陽極棒、３：端末治具、
４：メツキ液、５：循環ポンプ、６：配管、７：陰極、
８：洗浄水、９：超音波洗浄処理槽、１０：超音波振動
子、１１：モータ一 １２：通水管。FIG. 1 is an explanatory diagram showing a plating situation according to the present invention, and FIG. 2 is an explanatory diagram showing an ultrasonic cleaning process according to the same invention. 1: Zirconium alloy tube, 2: Anode rod, 3: Terminal jig,
4: Plating liquid, 5: Circulation pump, 6: Piping, 7: Cathode,
8: Cleaning water, 9: Ultrasonic cleaning treatment tank, 10: Ultrasonic vibrator, 11: Motor 12: Water pipe.
Claims (1)
に際して、メッキの前処理である酸洗活性化処理を、フ
ッ化アンモン０．２〜１．５モル、フッ酸０．０５〜０
．５モルの組成の、モル比がＮＨ＿４Ｆ／ＨＦ＝１．２
〜１５の酸洗液で行い、その後合金管の内面を超音波洗
浄処理し、メッキの際は合金管の中をメッキ液を循環さ
せながらメッキを行なうことを特徴とするジルコニウム
合金管の内面電気メッキ法。1 When electroplating metal on the inner surface of a zirconium alloy tube, pickling activation treatment, which is a pretreatment for plating, is performed using 0.2 to 1.5 mol of ammonium fluoride and 0.05 to 0.0 mol of hydrofluoric acid.
．． With a composition of 5 moles, the molar ratio is NH_4F/HF = 1.2
The inner surface of a zirconium alloy tube is characterized in that the inner surface of the alloy tube is subjected to ultrasonic cleaning treatment, and the plating is performed while circulating the plating solution inside the alloy tube during plating. Plating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53118273A JPS5948959B2 (en) | 1978-09-26 | 1978-09-26 | Internal electroplating method for zirconium alloy tubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53118273A JPS5948959B2 (en) | 1978-09-26 | 1978-09-26 | Internal electroplating method for zirconium alloy tubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5544575A JPS5544575A (en) | 1980-03-28 |
| JPS5948959B2 true JPS5948959B2 (en) | 1984-11-29 |
Family
ID=14732555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53118273A Expired JPS5948959B2 (en) | 1978-09-26 | 1978-09-26 | Internal electroplating method for zirconium alloy tubes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5948959B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56148916A (en) * | 1980-04-07 | 1981-11-18 | Asahi Chem Ind Co Ltd | Preparation of novel acrylic composite fiber |
| JPH0228713Y2 (en) * | 1985-10-16 | 1990-08-01 | ||
| JPH03173104A (en) * | 1989-11-30 | 1991-07-26 | Shin Etsu Chem Co Ltd | Manufacturing method of corrosion-resistant rare earth magnet |
| CN114540828A (en) * | 2022-03-23 | 2022-05-27 | 中国原子能科学研究院 | Method for electrodepositing uranium on metal surface |
-
1978
- 1978-09-26 JP JP53118273A patent/JPS5948959B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5544575A (en) | 1980-03-28 |
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