JPH04187779A - Formation of corrosion and wear resistant composite film on surface of metallic base material - Google Patents
Formation of corrosion and wear resistant composite film on surface of metallic base materialInfo
- Publication number
- JPH04187779A JPH04187779A JP31576790A JP31576790A JPH04187779A JP H04187779 A JPH04187779 A JP H04187779A JP 31576790 A JP31576790 A JP 31576790A JP 31576790 A JP31576790 A JP 31576790A JP H04187779 A JPH04187779 A JP H04187779A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- corrosion
- metal
- layer
- metallic base
- 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
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000005260 corrosion Methods 0.000 title claims abstract description 15
- 230000007797 corrosion Effects 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims description 6
- 230000015572 biosynthetic process Effects 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000007772 electroless plating Methods 0.000 claims abstract description 14
- 239000004020 conductor Substances 0.000 claims abstract description 4
- 239000012811 non-conductive material Substances 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 238000007789 sealing Methods 0.000 abstract description 4
- 229910000975 Carbon steel Inorganic materials 0.000 abstract description 3
- 239000010962 carbon steel Substances 0.000 abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 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
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910017083 AlN Inorganic materials 0.000 abstract 1
- 229910034327 TiC Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 16
- 238000007747 plating Methods 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- -1 18Cr-88i) Substances 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 229910005091 Si3N Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は金属基材の表面に耐食・耐摩耗性複合皮膜を形
成させる方法に関し２ 腐食性、摩耗性高温雰囲気中で
使用される配管、弁、タンク等の構成材料の製造に有利
に適用しつる同方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for forming a corrosion-resistant and wear-resistant composite film on the surface of a metal substrate. 2. Piping used in a corrosive and abrasive high-temperature atmosphere; The present invention relates to a method which can be advantageously applied to the manufacture of constituent materials for valves, tanks, etc.
従来、腐食性、摩耗性高温雰囲気中で摩耗特性を要求さ
れる場合には高ニッケル・クロム基合金、ステン）／ス
鋼などが使用されてい乙。Conventionally, high nickel-chromium based alloys, stainless steels, etc. have been used when wear characteristics are required in corrosive and abrasive high-temperature atmospheres.
高温下での腐食性および摩耗性環境において、従来の高
級材料に代るものとし７て炭素鋼なとパ）低級材料に耐
食耐摩耗性溶射皮膜の被覆し−こ゛耐食性、耐摩耗性機
能をもたらオー、ｌ！′が考λられているが、１ユの場
合の問題点と１，７て溶射被眼成分そのものは耐食性を
も−）もの６゛）溶射皮膜特有の微細な孔のため腐食性
溶液が金属基材パ、到達し、その結果、金属基材の腐食
ひいては溶射被膜の剥離を起こす二とがあげられる一１
従−１て腐食性溶液が溶射被膜に浸透１．でも耐久性に
乏し２い金属基材を防食（、得る皮膜の＠ ＩＪ’２お
５Ｌび製？シフ方法の開発が待たれでも）だ。In corrosive and abrasive environments at high temperatures, carbon steel can be used as an alternative to traditional high-grade materials. Bring it on, l! ' has been considered, but there are problems in the case of 1 U, and 1, 7, the thermal spray coating component itself is corrosion resistant. The metal particles reach the base material, resulting in corrosion of the metal base material and peeling of the sprayed coating.
1. Corrosive solution penetrates into the sprayed coating. However, it is good for corrosion protection of metal substrates that lack durability (IJ'2 and 5L are the most durable).
また従来、溶射層内に存在する空隙（孔）４満たす（封
孔）手段として、常温な（、・Ｌ、 １ （１０℃程度
までは樹脂等１．−よる有筬物封孔処理／・（なされて
いるが、使用環境が高温になる場合（を適用が困難であ
った。Conventionally, as a means of filling (sealing) the voids (pores) 4 existing in the sprayed layer, a reed material sealing process using resin, etc. 1. (Although it has been done, it was difficult to apply it when the usage environment becomes high temperature).
本発明は上記技術水準に２み、低級金属基材を腐食性、
摩耗性高温雰囲気中でも耐食性、耐摩耗性にすることが
できる方法を提供しようとするものである。The present invention is based on the above-mentioned state of the art.
The purpose is to provide a method that can provide corrosion resistance and wear resistance even in an abrasive high-temperature atmosphere.
本発明は金属基材の表面に、非導電性材料又は導電性材
料を溶射して溶射層を形成させた後、該溶射層の微細孔
内に無電解めっきにより金属を析出させて封孔すること
を特徴とする金属基材表面への耐食・耐摩耗性複合皮膜
の形成方法である。The present invention involves spraying a non-conductive material or a conductive material onto the surface of a metal base material to form a sprayed layer, and then depositing metal into the fine pores of the sprayed layer by electroless plating to seal the pores. This is a method for forming a corrosion-resistant and wear-resistant composite film on the surface of a metal substrate.
本発明でいう非導電性材料としてはＡｌ２Ｏ３。The non-conductive material used in the present invention is Al2O3.
Ａ１□０３・ＭｇＯ、ＡＩＮ 、 ＭｇＯ、ＭｇＯ・Ｓ
ｉＬ 、 ２Ｍｇ０・ＳｉＬ 、 ５ｉ０２． ＳｉＣ
、５ｉＣ−５ｉ３Ｎ１． ＢＮ 。A1□03・MgO, AIN, MgO, MgO・S
iL, 2Mg0・SiL, 5i02. SiC
, 5iC-5i3N1. BN.
ＺｒＯ２，Ｓｉ３Ｎ、 、 ＺｒＯ□・Ｓｉｎ、などが
あげられ、導電性材料としてはＦｅ、 Ｃｒ、 Ｎｉ
、 Ｚｎ、 Ｍｏ。Examples include ZrO2, Si3N, ZrO□・Sin, etc., and conductive materials include Fe, Cr, Ni
, Zn, Mo.
Ｔａ、Ｗ、Ａ１などの金属、低合金鋼、°ステンレス鋼
（例えば１８Ｃｒ−８８ｉ）、アルミニウム青銅、黄銅
などの合金、ＴｉＮ 、 Ｔｉｃ 、 ＴｌＢ２ 、
Ｃｒ２Ｏ３゜Ｃｒ３Ｃ２，Ｂ４Ｃ、ＷＣ、ＺｒＬなどの
セラミックスがあげられ、無電解めっきに使用する金属
としてはＮｉ 、 Ｐｂ 、 Ｃｕ 、 Ｐｔ 、 Ａ
ｇ 、 Ａｕなどがあげられる。Metals such as Ta, W, A1, low alloy steel, stainless steel (e.g. 18Cr-88i), alloys such as aluminum bronze, brass, TiN, Tic, TlB2,
Examples include ceramics such as Cr2O3゜Cr3C2, B4C, WC, and ZrL, and metals used for electroless plating include Ni, Pb, Cu, Pt, and A.
Examples include g, Au, etc.
無電解めっきとしては９０℃で行う高温タイプめっき浴
、６０℃又は３０℃で行う低温タイプめっき浴が使用さ
れ、それらの−例をあげると下表のものがある。For electroless plating, high-temperature plating baths carried out at 90°C and low-temperature plating baths carried out at 60°C or 30°C are used, examples of which are shown in the table below.
高温タイプのめっき浴
低温タイプのめっき浴
〔作用〕
本発明の耐食耐摩耗性複合皮膜は上記のように構成され
ており、最表層の耐摩耗性溶射皮膜のだめに摩耗が抑制
されるとともに、金属基材付近の溶射皮膜中の微細な空
隙は耐食性の金属めっきで満たされているため外部から
浸透する腐食性溶液を遮蔽して耐食性の乏しい金属基材
への到達を防止する。High-temperature type plating bath Low-temperature type plating bath [Function] The corrosion-resistant and wear-resistant composite coating of the present invention is constructed as described above, and wear is suppressed in the outermost layer of the wear-resistant thermal sprayed coating, and the metal The fine voids in the sprayed coating near the base material are filled with corrosion-resistant metal plating, which blocks corrosive solutions from penetrating from the outside and prevents them from reaching the metal base material, which has poor corrosion resistance.
次に、本発明の実施例を第１図、第２図および第３図に
より説明する。Next, embodiments of the present invention will be described with reference to FIGS. 1, 2, and 3.
第１図は耐食耐摩耗性複合被膜の形成方法に関する工程
図であり詳細に説明すると次のとおりである。FIG. 1 is a process diagram relating to a method for forming a corrosion-resistant and wear-resistant composite coating, and the details will be explained as follows.
まず、金属基材には炭素鋼などの低級材料を用い、これ
をブラスト処理により粗面化したのち、耐摩耗性の金属
、合金又はセラミックス材料を溶射する。First, a low-grade material such as carbon steel is used as the metal base material, and after roughening the surface by blasting, a wear-resistant metal, alloy, or ceramic material is thermally sprayed.
次に溶射層内の微細な空隙を塞ぐた狛耐食性がありかつ
緻密層を形成しやすいニッケル等の金属の無電解めっき
処理を行なう。ここで無電解めっきは通常６０℃又は９
０℃の高温でめっきが成長することから、溶射層内の金
属基材側から順次めっきするため、溶射層の金属基材部
と表層部に温度差を設けるよう工夫されている。Next, electroless plating of a metal such as nickel, which has corrosion resistance and is easy to form a dense layer, is performed to close the minute voids in the sprayed layer. Here, electroless plating is usually 60℃ or 9℃.
Since plating grows at a high temperature of 0° C., in order to sequentially plate from the metal base material side in the sprayed layer, it is devised to provide a temperature difference between the metal base portion and the surface layer of the sprayed layer.
すなわち、常温の無電解めっき液中に供試体を浸漬させ
溶射層内に充分にめっき液を含浸させたのち、一定時間
金属基材側を６０℃又は９０℃の無電解めっき条件に昇
温する。この含浸〜昇温をくり返すことにより目的のめ
っき層を金属基材側から成長させる。この間、溶射層外
部のめっき液は例えば２０〜２５℃の常温に調整してお
き、溶射層の外部からめっきが成長しないようにする必
要がある。That is, after immersing the specimen in an electroless plating solution at room temperature and sufficiently impregnating the plating solution into the sprayed layer, the metal substrate side is heated to 60°C or 90°C under electroless plating conditions for a certain period of time. . By repeating this process of impregnation and temperature rise, the desired plating layer is grown from the metal base material side. During this time, it is necessary to adjust the plating solution outside the sprayed layer to a normal temperature of, for example, 20 to 25°C to prevent the plating from growing from outside the sprayed layer.
実施例として無電解めっきによる反応式と液条件等をニ
ッケルの場合で説明する。As an example, the reaction formula and liquid conditions for electroless plating will be explained using nickel.
Ｎｌ”＋Ｈ２ＰＯ□→ Ｎｌ＋ Ｈ４Ｆ［］３−＋ ２
８”還元材 析出ニッケル
めっき条件（添加剤省略）
低温タイプ 高温タイプ
硫酸ニッケル ２６２５
（ｇ／β）
次亜リン酸 １１２１
（ｇ／Ｉり
ｐＨ（−）６〜７４．５〜５．５
温度 （ｔ） ６０ ９０第２図、
第３図には管及び板状の場合の無電解めっき手法の一実
施例を示す。Nl”+H2PO□→ Nl+ H4F[]3-+ 2
8" Reducing agent Precipitated nickel plating conditions (additives omitted) Low temperature type High temperature type Nickel sulfate 2625 (g/β) Hypophosphorous acid 1121 (g/I pH (-) 6-74.5-5.5 Temperature ( t) 60 90Figure 2,
FIG. 3 shows an example of an electroless plating method for pipes and plates.
第２図は管外表面に金属、合金又はセラミックス溶射し
たのちの無電解めっきの場合を示す。FIG. 2 shows the case of electroless plating after spraying a metal, alloy, or ceramic on the outer surface of the tube.
第２図において、１は管（金属基材）、２は溶射層、３
はプラグ、４は容器、５は熱電対（１）、６はチラー、
７はヒータ、８は攪拌機、９は無電解めっき液、１０は
温調器（１）、１１は温調器（２）、１２はヒータ電源
、１３はチラー電源、１４はモータ、１５はタイマー、
１９は熱電対（２）である。In Fig. 2, 1 is a tube (metal base material), 2 is a sprayed layer, and 3
is the plug, 4 is the container, 5 is the thermocouple (1), 6 is the chiller,
7 is a heater, 8 is a stirrer, 9 is an electroless plating solution, 10 is a temperature controller (1), 11 is a temperature controller (2), 12 is a heater power supply, 13 is a chiller power supply, 14 is a motor, 15 is a timer ,
19 is a thermocouple (2).
ここで、管ｌに施工された溶射層２の金属基材側から順
次めっきするため、金属基材側のみをめっき条件を満足
させるため内部からヒータ７により加熱する。また溶射
層の表層部は逆にめっきのできない条件とするた約、め
っき液を冷却する。Here, in order to sequentially plate the thermal sprayed layer 2 applied to the pipe 1 from the metal base material side, only the metal base material side is heated from the inside by the heater 7 in order to satisfy the plating conditions. On the other hand, the surface layer of the sprayed layer is kept under conditions that do not permit plating, and the plating solution is cooled.
それぞれの温度の調整は溶射層の内部と外部は別々に行
う。Each temperature is adjusted separately for the inside and outside of the sprayed layer.
第３図は板状の場合の実施例を示す。FIG. 3 shows an embodiment in the case of a plate shape.
第３図において、１７は金属板、１６はクランプであり
、その他の符号は第２図と同じものを示す。In FIG. 3, 17 is a metal plate, 16 is a clamp, and other symbols are the same as in FIG. 2.
この場合は架設のめっき槽の底部として供試体を用いる
か、又は金属基材裏面をシールする必要がある。In this case, it is necessary to use the specimen as the bottom of an erected plating bath, or to seal the back surface of the metal substrate.
本発明により、低級材料を耐食耐摩耗性を備えた材料と
することができるとともに高温環境下での使用が可能と
なり価格の点からも適用範囲が大巾に拡大する。According to the present invention, a low-grade material can be made into a material with corrosion resistance and wear resistance, and it can also be used in a high-temperature environment, which greatly expands the range of applications in terms of cost.
又溶射膜の密着力向上にも寄与し、かつ封孔技術の発展
にも寄与する。It also contributes to improving the adhesion of thermally sprayed films and to the development of pore sealing technology.
第１図は本発明の工程図表、第２図及び第３図は本発明
方法を実施する装置の概略図である。FIG. 1 is a process diagram of the present invention, and FIGS. 2 and 3 are schematic diagrams of an apparatus for carrying out the method of the present invention.
Claims (1)
射して溶射層を形成させた後、該溶射層の微細孔内に無
電解めっきにより金属を析出させて封孔することを特徴
とする金属基材表面への耐食・耐摩耗性複合皮膜の形成
方法。It is characterized by forming a sprayed layer by spraying a non-conductive material or a conductive material onto the surface of a metal base material, and then depositing metal into the fine pores of the sprayed layer by electroless plating to seal the pores. A method for forming a corrosion-resistant and wear-resistant composite film on the surface of a metal substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31576790A JPH04187779A (en) | 1990-11-22 | 1990-11-22 | Formation of corrosion and wear resistant composite film on surface of metallic base material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31576790A JPH04187779A (en) | 1990-11-22 | 1990-11-22 | Formation of corrosion and wear resistant composite film on surface of metallic base material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04187779A true JPH04187779A (en) | 1992-07-06 |
Family
ID=18069302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31576790A Pending JPH04187779A (en) | 1990-11-22 | 1990-11-22 | Formation of corrosion and wear resistant composite film on surface of metallic base material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04187779A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1289038A2 (en) * | 2001-08-29 | 2003-03-05 | Araco Kabushiki Kaisha | Manufacturing method of anti-corrosive multi-layered structure material |
| US8482132B2 (en) * | 2009-10-08 | 2013-07-09 | International Business Machines Corporation | Pad bonding employing a self-aligned plated liner for adhesion enhancement |
| CN110055483A (en) * | 2019-06-10 | 2019-07-26 | 河海大学 | A method of improving titanium nitride-titanium oxide composite coating corrosion resistance |
-
1990
- 1990-11-22 JP JP31576790A patent/JPH04187779A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1289038A2 (en) * | 2001-08-29 | 2003-03-05 | Araco Kabushiki Kaisha | Manufacturing method of anti-corrosive multi-layered structure material |
| JP2003073847A (en) * | 2001-08-29 | 2003-03-12 | Araco Corp | Method for manufacturing bilayer structural material with corrosion resistance |
| EP1289038A3 (en) * | 2001-08-29 | 2004-01-07 | Araco Kabushiki Kaisha | Manufacturing method of anti-corrosive multi-layered structure material |
| US6737104B2 (en) | 2001-08-29 | 2004-05-18 | Araco Kabushiki Kaisha | Manufacturing method of anti-corrosive multi-layered structure material |
| US8482132B2 (en) * | 2009-10-08 | 2013-07-09 | International Business Machines Corporation | Pad bonding employing a self-aligned plated liner for adhesion enhancement |
| CN110055483A (en) * | 2019-06-10 | 2019-07-26 | 河海大学 | A method of improving titanium nitride-titanium oxide composite coating corrosion resistance |
| CN110055483B (en) * | 2019-06-10 | 2021-04-09 | 河海大学 | Method for improving corrosion resistance of titanium nitride-titanium oxide composite coating |
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