JPS6357783A - Zirconium alloy articles having chemically compacted ceramic film - Google Patents

Zirconium alloy articles having chemically compacted ceramic film

Info

Publication number
JPS6357783A
JPS6357783A JP19994986A JP19994986A JPS6357783A JP S6357783 A JPS6357783 A JP S6357783A JP 19994986 A JP19994986 A JP 19994986A JP 19994986 A JP19994986 A JP 19994986A JP S6357783 A JPS6357783 A JP S6357783A
Authority
JP
Japan
Prior art keywords
zirconium alloy
oxide
film
pretreatment
alloy articles
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.)
Pending
Application number
JP19994986A
Other languages
Japanese (ja)
Inventor
Hiroshi Kawamura
弘 河村
Ikuyoshi Miyajima
生欣 宮島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TOOKARO KK
Tocalo Co Ltd
Japan Atomic Energy Agency
Original Assignee
TOOKARO KK
Tocalo Co Ltd
Japan Atomic Energy Research Institute
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TOOKARO KK, Tocalo Co Ltd, Japan Atomic Energy Research Institute filed Critical TOOKARO KK
Priority to JP19994986A priority Critical patent/JPS6357783A/en
Publication of JPS6357783A publication Critical patent/JPS6357783A/en
Pending legal-status Critical Current

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  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

PURPOSE:To produce zirconium alloy articles having resistance to hydrogen embrittlement by forming the film of oxide consisting of ZrO2 by a pretreatment on the surface of a zirconium alloy and coating the surface of the oxide with various kinds of chemically compacted composite ceramic layers by a pretreatment. CONSTITUTION:The film 2 of the oxide consisting of the ZrO2 is formed by the pretreatment on the surface 1' of the zirconium alloy material 1 having various shapes. The composite ceramic layers 3 of various kinds (SiO2, Al2O3, Cr2O3 or other ceramics) are coated on the surface 2' of such oxide film 2. The composite ceramic layers 3 are then treated by a chromic compd. and are thereby chemically compacted. The zirconium alloy articles which have the high resistance to hydrogen embrittlement and are usable in a hydrogen atmosphere are thereby obtd.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は化学的に緻密化されたセラミックス皮膜を有す
るジルコニウム合金製物品に関する。
DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a zirconium alloy article having a chemically densified ceramic coating.

(従来の技術) FGに、ジルコニウム合金は、水素雰囲気中において水
素化物を形成して脆化する材料である。
(Prior Art) Zirconium alloys in FG are materials that form hydrides and become brittle in a hydrogen atmosphere.

ジルコニウム合金製物品は、そのため、従来からそのよ
うな雰囲気中では使用されていない状態にあった。
Zirconium alloy articles have therefore traditionally not been used in such atmospheres.

(発明が解決しようとする問題点) 本発明の目的は、ジルコニウム合金製物品の上記の欠点
を解決し、耐水素脆化性を有する化学的に緻密化された
各種複合セラミックスを皮膜したジルコニウム合金製物
品を提供することである。
(Problems to be Solved by the Invention) The object of the present invention is to solve the above-mentioned drawbacks of articles made of zirconium alloys, and to solve the above-mentioned drawbacks of articles made of zirconium alloys. The goal is to provide manufactured goods.

(問題点を解決するための手段) このような目的は、本発明に依って、前処理によってZ
r0zから成る酸化物を形成してなるジルコニウム合金
表面の酸化物表面上に、更にクロム化合物によって化学
的に緻密化されたSiO2、Al2O3及びCr2O2
、あるいは他のセラミックスから成る組成を有する皮膜
を被覆構成せしめ°ζなることを特徴とするジルコニウ
ム合金製物品によって達成される。即ち、本発明のジル
コニウム合金製物品は、ジルコニウム合金材の表面に、
中間層としてZrO□から成る酸化膜を介在せしめ、且
つその上に複合セラミックス自体の緻ε性に相乗して極
めて効果的に構成し得るものである。
(Means for solving the problem) According to the present invention, this purpose
SiO2, Al2O3 and Cr2O2 chemically densified with a chromium compound on the oxide surface of the zirconium alloy surface formed by forming an oxide consisting of r0z.
This is achieved by a zirconium alloy article characterized by being coated with a film having a composition consisting of , or other ceramics. That is, in the zirconium alloy article of the present invention, on the surface of the zirconium alloy material,
An oxide film made of ZrO□ is interposed as an intermediate layer, and the structure can be extremely effectively achieved by interposing an oxide film made of ZrO□ on top of the oxide film, which is synergistic with the fineness of the composite ceramic itself.

本発明を、第1図及び第2図について、さらに詳細に説
明する。
The invention will now be described in more detail with reference to FIGS. 1 and 2.

各種の形状のジルコニウム合金材(1)の表面(l゛)
に前処理によってZrO□から成る酸化膜を皮膜し、そ
の酸化膜表面(2゛)上にクロム化合物によって化学的
に緻密化された各種(SiO□、Al2O2及びCr2
O3、あるいは他のセラミックス)の複合セラミックス
N(3)を被覆構成したものである。
Surfaces (l゛) of zirconium alloy materials (1) of various shapes
An oxide film consisting of ZrO□ is formed by pretreatment on the oxide film, and on the surface (2゛) of the oxide film, various types (SiO□, Al2O2 and Cr2) chemically densified with chromium compounds are coated.
It is coated with a composite ceramic N(3) of O3 or other ceramics).

(実施例) その製造工程を実施例例によって詳細に説明する。(Example) The manufacturing process will be explained in detail with reference to Examples.

夫1」虹−上 (11ジルコニウム合金の前処理工程 ジルカロイ−4製板材(巾30mm x長さ50mm 
x厚さ2mm)の全面にオートクレーブ処理により膜厚
約3mn+のZrO2皮膜を形成した。
Husband 1" Rainbow - Top (11 Pre-treatment process of zirconium alloy Zircaloy-4 plate material (width 30 mm x length 50 mm
A ZrO2 film with a thickness of about 3 mm+ was formed on the entire surface of the sample (x 2 mm thick) by autoclave treatment.

(2)セラミックス・スラリーの3周製50重景%のC
ry、水溶液に平均粒径10μmのSiO□粉末を重量
比1:lに混合し、磁性ボールミルを用いて18時間混
練し、スラリーを調製した。
(2) 3 laps of ceramic slurry 50% C
SiO□ powder having an average particle size of 10 μm was mixed into the aqueous solution at a weight ratio of 1:1 and kneaded for 18 hours using a magnetic ball mill to prepare a slurry.

(3)コーティング工程 上記スラリー中にオートクレーブ処理されたジルカロイ
−4板材を浸漬して塗装し、100〜200℃で乾燥さ
せた後、電気炉を用いて600’C/時間で昇温し、5
50℃で1時間保持し、100 ’C/時間で降温冷却
した。
(3) Coating process An autoclaved Zircaloy-4 plate was dipped in the above slurry, dried at 100 to 200°C, and then heated at 600°C/hour using an electric furnace.
The temperature was maintained at 50° C. for 1 hour, and the temperature was lowered and cooled at 100° C./hour.

(4)酸化クロム充填工程 ■Cr01水溶液(比重1.30〜1.70)含浸、■
 加熱焼成(昇温600℃)時間、550’Cテ1時間
保持、降温100℃7時間) ■ ■〜■の工程を8〜15回繰り返す。
(4) Chromium oxide filling process ■ Impregnation with Cr01 aqueous solution (specific gravity 1.30 to 1.70), ■
Heating and firing (temperature increase: 600°C) time, hold at 550'C for 1 hour, temperature decrease: 100°C for 7 hours) ① Repeat steps ① to ② 8 to 15 times.

実呈±−I (1)ジルコニウム合金の前処理工程 実施例1に同じ (2)セラミックス・スラリーの調製 50重量%のCrux水溶液に、それと同重量で重量比
1:1のSingとY2O3安定化Zr0zの粉末を混
合し、磁性ボールミルを用いて30時間混練し、スラリ
ーを調製した。
Demonstration ±-I (1) Zirconium alloy pretreatment process Same as Example 1 (2) Preparation of ceramic slurry 50% by weight aqueous Crux solution and the same weight of Sing and Y2O3 stabilization at a weight ratio of 1:1 Zr0z powder was mixed and kneaded for 30 hours using a magnetic ball mill to prepare a slurry.

(3)コーティング工程 実施例1に同じ (4)酸化クロム充填工程 実施例1に同じ このように形成されらた皮膜の断面顕微鏡写真を第3図
に示す。
(3) Coating process Same as Example 1 (4) Chromium oxide filling process Same as Example 1 A cross-sectional micrograph of the film thus formed is shown in FIG.

第3図は、本発明のジルコニウム合金材の表面に形成さ
れた疼膜の断面顕微鏡写真で、ジルコニウム合金母材(
1)上に、Zr0z皮膜(2)が形成されており、その
上に緻密化された複合セラミックス皮膜(3)が形成さ
れている状態が示されている。
FIG. 3 is a cross-sectional micrograph of the tunica formed on the surface of the zirconium alloy material of the present invention.
1), a Zr0z film (2) is formed thereon, and a densified composite ceramic film (3) is formed thereon.

本発明のジルコニウム合金製物品とジルコニウム合金と
の主たる特性を第1表に示す。
Table 1 shows the main properties of the zirconium alloy article and zirconium alloy of the present invention.

拐1 マイクロピッ カース硬度  電気伝導度 皮膜密着力 熱衝撃試験(
100gf)    (Ω−’cm)   (Kg/c
m”)  400 ”C−*水中ジルカロイー4  2
00    2.1xlO’    −−
Test 1 Micropicker hardness Electrical conductivity Film adhesion Thermal shock test (
100gf) (Ω-'cm) (Kg/c
m") 400 "C-* Zircaloy in water 4 2
00 2.1xlO' --

【図面の簡単な説明】[Brief explanation of drawings]

第1図及び第2図は本発明の一具体例における構成の説
明図である。 第3図は本発明のジルコニウム合金製物品の断面顕微鏡
写真である。
FIGS. 1 and 2 are explanatory diagrams of a configuration in a specific example of the present invention. FIG. 3 is a cross-sectional micrograph of the zirconium alloy article of the present invention.

Claims (1)

【特許請求の範囲】[Claims] 前処理によってZrO_2から成る酸化物(2)を形成
してなるジルコニウム合金表面(1)の酸化物表面上に
、更にクロム化合物によって化学的に緻密化されたSi
O_2、Al_2O_3及びCr_2O_3、あるいは
他のセラミックスから成る組成を有する皮膜(3)を被
覆構成せしめてなることを特徴とするジルコニウム合金
製物品。
On the oxide surface of the zirconium alloy surface (1) formed by forming an oxide (2) consisting of ZrO_2 through pretreatment, Si is further chemically densified with a chromium compound.
A zirconium alloy article characterized in that it is coated with a coating (3) having a composition of O_2, Al_2O_3, Cr_2O_3, or other ceramics.
JP19994986A 1986-08-28 1986-08-28 Zirconium alloy articles having chemically compacted ceramic film Pending JPS6357783A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP19994986A JPS6357783A (en) 1986-08-28 1986-08-28 Zirconium alloy articles having chemically compacted ceramic film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP19994986A JPS6357783A (en) 1986-08-28 1986-08-28 Zirconium alloy articles having chemically compacted ceramic film

Publications (1)

Publication Number Publication Date
JPS6357783A true JPS6357783A (en) 1988-03-12

Family

ID=16416278

Family Applications (1)

Application Number Title Priority Date Filing Date
JP19994986A Pending JPS6357783A (en) 1986-08-28 1986-08-28 Zirconium alloy articles having chemically compacted ceramic film

Country Status (1)

Country Link
JP (1) JPS6357783A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5411247A (en) * 1977-06-25 1979-01-27 Japan Maize Prod Production of oil and fat processed starch
JPS58189318A (en) * 1982-04-28 1983-11-05 Mazda Motor Corp Electric heating type heat treatment furnace
JPS59157284A (en) * 1983-02-18 1984-09-06 シーメンス、アクチエンゲゼルシヤフト Surface treatment of zirconium alloy parts for nuclear reactor fuel assembly

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5411247A (en) * 1977-06-25 1979-01-27 Japan Maize Prod Production of oil and fat processed starch
JPS58189318A (en) * 1982-04-28 1983-11-05 Mazda Motor Corp Electric heating type heat treatment furnace
JPS59157284A (en) * 1983-02-18 1984-09-06 シーメンス、アクチエンゲゼルシヤフト Surface treatment of zirconium alloy parts for nuclear reactor fuel assembly

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