JPS6357783A - Zirconium alloy articles having chemically compacted ceramic film - Google Patents
Zirconium alloy articles having chemically compacted ceramic filmInfo
- 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
Links
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 24
- 239000000919 ceramic Substances 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 150000001845 chromium compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 239000002002 slurry Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
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' --
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)
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.
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)
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 |
-
1986
- 1986-08-28 JP JP19994986A patent/JPS6357783A/en active Pending
Patent Citations (3)
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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