JPH07180029A - Corrosion resistant material and its production - Google Patents
Corrosion resistant material and its productionInfo
- Publication number
- JPH07180029A JPH07180029A JP32784893A JP32784893A JPH07180029A JP H07180029 A JPH07180029 A JP H07180029A JP 32784893 A JP32784893 A JP 32784893A JP 32784893 A JP32784893 A JP 32784893A JP H07180029 A JPH07180029 A JP H07180029A
- Authority
- JP
- Japan
- Prior art keywords
- zirconium
- substrate
- film
- zirconium nitride
- resistant material
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は薄膜電極材料等に汎用さ
れている耐食性材料及びその製造方法に関するものであ
り、詳細には無機材料又は金属材料基板上に窒化ジルコ
ニウムの皮膜を付したものである。本発明により得られ
た耐食性材料は腐食性溶液中であっても優れた耐食性を
示す。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a corrosion resistant material generally used for thin film electrode materials and the like and a method for producing the same, and more particularly to an inorganic material or metal material substrate coated with a zirconium nitride film. is there. The corrosion resistant material obtained according to the present invention exhibits excellent corrosion resistance even in a corrosive solution.
【０００２】[0002]
【従来の技術】従来より薄膜を形成する技術としてスパ
ッタリングがよく用いられている。スパッタリングと
は、真空容器内に導入したアルゴン等の不活性ガスをイ
オン化し、そのイオンをターゲットと呼ばれる固体試料
表面に衝撃させ、ターゲットの原子をはじき出して基材
上に付着させる薄膜作成法である。2. Description of the Related Art Conventionally, sputtering has been often used as a technique for forming a thin film. Sputtering is a method of forming a thin film in which an inert gas such as argon introduced into a vacuum container is ionized, and the ions are bombarded on the surface of a solid sample called a target, and the atoms of the target are ejected and adhered onto a substrate. .
【０００３】スパッタリングのうち、反応性スパッタリ
ングとは、スパッタ蒸着の実施と同時にターゲット物質
とスパッタガス成分を化学反応させ、その生成物質を基
材上に薄膜として形成するものであり、金属の窒化物、
酸化物、或は炭化物等の薄膜の形成に広く用いられてい
る。Among the sputtering methods, the reactive sputtering method is a method in which a target substance and a sputter gas component are chemically reacted with each other at the same time as the sputter deposition is performed, and the generated substance is formed as a thin film on a substrate. ,
It is widely used for forming thin films of oxides or carbides.
【０００４】反応性スパッタリングを利用して窒化ジル
コニウム皮膜を形成したものは従来より耐食性材料とし
て用いられており、下記文献(1),(2),(3) にはこの窒化
ジルコニウム皮膜が基材（金属材料等）を保護する防食
皮膜として作用していることについて開示されている。A zirconium nitride film formed by using reactive sputtering has been conventionally used as a corrosion resistant material. In the following documents (1), (2) and (3), this zirconium nitride film is used as a base material. It is disclosed that it acts as an anticorrosion film for protecting (metal materials and the like).
【０００５】(1) U.K.Wiiala et al.,Surface and Coat
ings Tech.,41,(1990),191 (2) L.van Leaven et al.,Surface and Coatings Tec
h.,53,(1992),25 (3) Markke Tavi et al.,Material Sci.Foeum,44＆ 45,
(1989),15(1) UKWiiala et al., Surface and Coat
ings Tech., 41, (1990), 191 (2) L. van Leaven et al., Surface and Coatings Tec
h., 53, (1992), 25 (3) Markke Tavi et al., Material Sci. Foeum, 44 & 45,
(1989), 15
【０００６】[0006]
【発明が解決しようとする課題】以上の様に窒化ジルコ
ニウムを防食皮膜として利用することについては上記の
様に種々の研究成果が知られているが、従来技術はもっ
ぱら皮膜の欠陥を防止するという方向、即ち欠陥を生じ
ない様な構造上の改良という観点から開発や改良がなさ
れており、窒化ジルコニウム皮膜自身の特性という観点
から詳しく調べられていなかった。これは、皮膜自身の
耐食性よりも、皮膜に生じるピンホール等の欠陥の多少
の方が、防食特性に大きく影響すると考えられていたか
らである。As described above, various research results have been known regarding the use of zirconium nitride as an anticorrosion coating, but the prior art is exclusively for preventing the defects of the coating. It has been developed and improved in the direction, that is, from the viewpoint of structural improvement that does not cause defects, and has not been examined in detail from the viewpoint of the characteristics of the zirconium nitride film itself. This is because it was believed that some of the defects such as pinholes generated in the coating had a greater effect on the anticorrosion property than the corrosion resistance of the coating itself.
【０００７】本発明は上記事情に鑑みてなされたもので
あり、窒化ジルコニウム皮膜自身について検討を行い、
耐食性が向上した窒化ジルコニウム皮膜を有する耐食性
材料及びその製造方法を提供することを目的とする。The present invention has been made in view of the above circumstances, and the zirconium nitride film itself was examined,
An object of the present invention is to provide a corrosion resistant material having a zirconium nitride coating with improved corrosion resistance and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明に係る耐食性材料
の窒化ジルコニウム皮膜は格子定数が４．６０Å以下の
ものである。また本発明に係る耐食性材料の製造方法
は、金属ジルコニウムをターゲットとし、アルゴンガス
分圧に対する窒素ガス分圧の比を０．０３５以上として
反応性スパッタリングを行なったものである。更にはス
パッタ時のアルゴンガス分圧と窒素ガス分圧の和を５×
１０-2〜５×１０-4とし、基材温度は、セラミックス系
基材では常温〜１００℃、金属系基材では常温〜５００
℃とするのが好ましい。The zirconium nitride film of the corrosion resistant material according to the present invention has a lattice constant of 4.60Å or less. The method for producing a corrosion-resistant material according to the present invention is a method in which reactive sputtering is performed by using metallic zirconium as a target and setting the ratio of the partial pressure of nitrogen gas to the partial pressure of argon gas to 0.035 or more. Furthermore, the sum of the argon gas partial pressure and the nitrogen gas partial pressure during sputtering is 5 ×.
The temperature of the base material is set to 10 −2 to 5 × 10 −4 , and the base material temperature is normal temperature to 100 ° C. for the ceramic base material, and the normal temperature to 500 for the metal base material.
It is preferably set to ° C.
【０００９】[0009]
【作用】本発明者らは窒化ジルコニウム皮膜自身の特性
について鋭意検討した結果、皮膜の構造特性が耐食性に
大きく関与していることを見出した。つまり金属窒化物
皮膜の耐食性は、皮膜中の窒素と金属原子の化学組成
比、及び皮膜を構成する化合物の相に大きく依存すると
いう知見を得たのである。皮膜自身の耐食性を著しく向
上させるには、窒化ジルコニウムの場合、窒化ジルコ
ニウムの単相であることとし、皮膜中の窒素とジルコ
ニウムの比が１に近い化合物を合成するのが良い。この
様な窒化ジルコニウム皮膜は格子定数で言うと４．６０
Å以下のものに当たる。The present inventors have made earnest studies on the characteristics of the zirconium nitride coating itself, and as a result, have found that the structural characteristics of the coating have a great influence on the corrosion resistance. That is, it has been found that the corrosion resistance of the metal nitride coating largely depends on the chemical composition ratio of nitrogen and metal atoms in the coating and the phase of the compound constituting the coating. In order to remarkably improve the corrosion resistance of the film itself, in the case of zirconium nitride, it is preferable to use a single phase of zirconium nitride and synthesize a compound in which the ratio of nitrogen to zirconium in the film is close to 1. Such a zirconium nitride film has a lattice constant of 4.60.
Å Hit the following:
【００１０】またこの様な皮膜を作製する為には、窒素
分圧が最も重要な条件となることを見出し、この成膜条
件を詳細に調査した。図１はスパッタリング装置の一例
を示すＲＦマグネトロンスパッタリング装置の模式図で
ある。図中、４は基板（基材）、３は金属ジルコニウム
ターゲット、１０はアルゴン＋窒素プラズマの領域を示
し、９はジルコニウム粒子である。７は窒素ガスのボン
ベ、８はアルゴンガスのボンベ、５，６は流量計で、夫
々窒素ガス、アルゴンガスの流量を調節する。２は真空
ポンプ、１はＲＦ電源である。Further, it was found that the nitrogen partial pressure is the most important condition for producing such a film, and the film forming condition was investigated in detail. FIG. 1 is a schematic diagram of an RF magnetron sputtering apparatus showing an example of the sputtering apparatus. In the figure, 4 is a substrate (base material), 3 is a metal zirconium target, 10 is a region of argon + nitrogen plasma, and 9 is a zirconium particle. Reference numeral 7 is a nitrogen gas cylinder, 8 is an argon gas cylinder, and 5 and 6 are flowmeters for adjusting the flow rates of nitrogen gas and argon gas, respectively. 2 is a vacuum pump and 1 is an RF power supply.
【００１１】通常、スパッタリングでは窒化ジルコニウ
ム以外にジルコニウムも被覆されるが、皮膜中の窒素比
を増加させて窒化ジルコニウムの単相を形成するには、
スパッタリング時に窒素ガスの分圧を増加させ、プラズ
マ中の窒素を効率よく窒化ジルコニウムの形で皮膜中に
取り込むことが必要である。Although zirconium is usually coated in addition to zirconium nitride by sputtering, in order to increase the nitrogen ratio in the coating to form a single phase of zirconium nitride,
It is necessary to increase the partial pressure of nitrogen gas during sputtering so that nitrogen in the plasma can be efficiently incorporated into the film in the form of zirconium nitride.
【００１２】そこで本発明方法の様にアルゴンガスに対
する窒素ガスのガス圧力の比［Ｐ（Ｎ2)／Ｐ（Ａｒ）］
を０．０３５以上とすれば、窒素とジルコニウムの比が
１に近い窒化ジルコニウム単相の皮膜が形成できる。ま
たスパッタリングされたジルコニウム原子のプラズマ中
を通過する距離が長い程、プラズマ中の窒素原子とジル
コニウム原子が結合し易くなり、窒化ジルコニウム皮膜
の形成に好適である。Therefore, as in the method of the present invention, the ratio of the gas pressure of nitrogen gas to argon gas [P (N 2 ) / P (Ar)]
When the ratio is 0.035 or more, a zirconium nitride single-phase film having a nitrogen-zirconium ratio close to 1 can be formed. Further, the longer the distance of the sputtered zirconium atoms passing through the plasma, the easier the bonding of the nitrogen atoms and zirconium atoms in the plasma, which is suitable for forming the zirconium nitride film.
【００１３】作製された皮膜中の窒素とジルコニウムの
比は、格子定数から推定することが可能であり、窒素と
ジルコニウムの比が１に近い格子定数４．６０Å以下の
窒化ジルコニウム皮膜を形成できる。The ratio of nitrogen to zirconium in the formed film can be estimated from the lattice constant, and a zirconium nitride film having a lattice constant of 4.60Å or less, in which the ratio of nitrogen to zirconium is close to 1, can be formed.
【００１４】Ｐ（Ｎ2)／Ｐ（Ａｒ）ガス圧力比が上記
０．０３５より小さい場合は、形成された皮膜は窒化ジ
ルコニウムと金属ジルコニウムの混合相となり耐食性が
低いものとなる。When the P (N 2 ) / P (Ar) gas pressure ratio is smaller than 0.035, the formed film becomes a mixed phase of zirconium nitride and metallic zirconium and has low corrosion resistance.
【００１５】尚、Ｐ（Ｎ2)／Ｐ（Ａｒ）ガス圧力比が
０．０５より大きい場合は、耐食性は優れたものになる
が、成膜速度が極端に遅くなるため、実際のプロセスに
は不向きである。If the P (N 2 ) / P (Ar) gas pressure ratio is larger than 0.05, the corrosion resistance will be excellent, but the film forming rate will be extremely slow, so that the actual process will be impractical. Is not suitable for.
【００１６】皮膜と基材の密着性は、皮膜に生じる内部
応力、及び皮膜と基材の熱膨張率の差に大きく依存する
と考えられるが、本発明の方法、即ちＰ（Ｎ2)／Ｐ（Ａ
ｒ）ガス圧力比０．０３５以上で作製した皮膜は、基材
が珪酸ガラス、シリコンウエハ、Ｔｉ−６Ａｌ−４Ｖの
いずれの場合においても、密着性良く形成されることが
実験により確かめられた。即ち本発明方法では内部応力
の少ない膜が形成されているものと考えられる。It is considered that the adhesion between the coating and the substrate largely depends on the internal stress generated in the coating and the difference in the coefficient of thermal expansion between the coating and the substrate. However, the method of the present invention, that is, P (N 2 ) / P (A
r) Experiments have confirmed that the film formed with a gas pressure ratio of 0.035 or more is formed with good adhesion regardless of whether the substrate is silicate glass, a silicon wafer, or Ti-6Al-4V. That is, it is considered that the method of the present invention forms a film having less internal stress.
【００１７】また上記基材は熱膨張率が、珪酸ガラス：
０．５×１０-6／℃、シリコンウエハ：４．１５×１０
-6／℃、Ｔｉ−６Ａｌ−４Ｖ：９×１０-6／℃であり、
窒化ジルコニウム皮膜：７×１０-6／℃とは大きく異な
るが、本発明の窒化ジルコニウム皮膜はこれら基材に対
しても剥離することなく密着性良く作製できる。一方、
Ｐ（Ｎ2)／Ｐ（Ａｒ）ガス圧力比が０．０３５より小さ
い場合で作製された皮膜は、実験によれば基材より容易
に剥離するものであった。The above-mentioned substrate has a coefficient of thermal expansion of silicate glass:
0.5 × 10 −6 / ° C., silicon wafer: 4.15 × 10
-6 / ° C, Ti-6Al-4V: 9 x 10 -6 / ° C,
Zirconium nitride film: Although it is significantly different from 7 × 10 −6 / ° C., the zirconium nitride film of the present invention can be produced with good adhesion to these substrates without peeling. on the other hand,
According to the experiment, the film produced when the P (N 2 ) / P (Ar) gas pressure ratio was smaller than 0.035 was easily peeled from the substrate.
【００１８】またスパッタ時のアルゴンガス分圧と窒素
ガス分圧の和は５×１０-2〜５×１０-4とするのが望ま
しい。これは５×１０-2を超えた場合、スパッタ原子が
基板（基材）に到達せず、成膜ができなくなるためであ
り、一方５×１０-4を下回った場合、プラズマが発生せ
ずこの場合も成膜ができなくなるためである。Further, the sum of the partial pressure of argon gas and the partial pressure of nitrogen gas at the time of sputtering is preferably 5 × 10 -2 to 5 × 10 -4 . This is because when the concentration exceeds 5 × 10 -2 , sputtered atoms do not reach the substrate (base material) and film formation cannot be performed. On the other hand, when the concentration is less than 5 × 10 -4 , plasma is not generated. This is because the film formation cannot be performed in this case as well.
【００１９】スパッタ時の基材温度は、セラミックス系
の基材の場合、常温〜１００℃が好ましい。１００℃を
超える高温では、基材と窒化ジルコニウム皮膜の熱膨張
率の差によって剥離が生じるため、この範囲とした。ま
た金属系の基材の場合、スパッタ時の基材温度は常温〜
５００℃が好ましい。この範囲としたのは、５００℃を
超えた高温では基材の機械的性質が劣化するからであ
る。The substrate temperature during sputtering is preferably room temperature to 100 ° C. in the case of a ceramic-based substrate. At a high temperature exceeding 100 ° C., peeling occurs due to the difference in the coefficient of thermal expansion between the base material and the zirconium nitride film, so the range was set to this range. In the case of metal-based substrates, the substrate temperature during sputtering is room temperature to
500 ° C. is preferred. This range is set because the mechanical properties of the base material are deteriorated at a high temperature exceeding 500 ° C.
【００２０】尚、本発明においては上述の様に皮膜自身
の改善を主目的として提案しているが、本発明を実際の
部材に適用する場合には、皮膜欠陥をなくす方向或は少
なくする方向の技術を併用する方が、より望ましいこと
は言うまでもない。In the present invention, the main purpose of the invention is to improve the film as described above. However, when the present invention is applied to actual members, there is a direction to eliminate or reduce film defects. It goes without saying that it is more desirable to use the above technique together.
【００２１】[0021]
【実施例】ＲＦマグネトロンスパッタリング装置（図
１）を用い、下記の条件で基板（基材）上に反応性スパ
ッタリング法によって窒化ジルコニウム皮膜を形成した
（試料Ｎｏ．１〜９）。EXAMPLE A zirconium nitride film was formed on a substrate (base material) by a reactive sputtering method under the following conditions using an RF magnetron sputtering device (FIG. 1) (Sample Nos. 1 to 9).
【００２２】基板 ：珪酸ガラス ターゲット：金属ジルコニウム スパッタ時のアルゴンガス分圧と窒素ガス分圧の和：５
×１０-3ｔｏｒｒ Ｐ（Ｎ2)／Ｐ（Ａｒ）ガス圧力比：０〜０．０６（下記
表１参照） 基板温度：１００℃ 成膜時間：２時間Substrate: Silicate glass Target: Metal zirconium Sum of partial pressures of argon gas and nitrogen gas during sputtering: 5
× 10 −3 torr P (N 2 ) / P (Ar) gas pressure ratio: 0 to 0.06 (see Table 1 below) Substrate temperature: 100 ° C. Film formation time: 2 hours
【００２３】各試料皮膜について、Ｘ線回折を行ないそ
の構造から格子定数を求め、また生成相の同定を行なっ
た。更に成膜後の皮膜の剥離状況から、密着性の評価を
行なった。また５％塩酸水溶液中で分極測定を行ない、
自然浸漬電位での腐食電流及び不働態保持電流密度を測
定し、腐食電流から腐食速度を求め、これらから皮膜自
身の耐食性を評価した。下記表１にそれらの結果、及び
色調を示す。尚、Ｐ（Ｎ2)／Ｐ（Ａｒ）ガス圧力比が
０．０５より大きい場合では、成膜速度が遅いため、試
料の評価ができなかった。For each sample film, X-ray diffraction was performed to determine the lattice constant from its structure, and the produced phase was identified. Further, the adhesion was evaluated based on the state of peeling of the film after film formation. In addition, polarization measurement was performed in a 5% hydrochloric acid aqueous solution.
The corrosion current at the natural immersion potential and the passivation current density were measured, the corrosion rate was calculated from the corrosion current, and the corrosion resistance of the film itself was evaluated from these. The results and the color tone are shown in Table 1 below. When the P (N 2 ) / P (Ar) gas pressure ratio was greater than 0.05, the sample could not be evaluated because the film formation rate was slow.
【００２４】[0024]
【表１】 [Table 1]
【００２５】格子定数については、Ｐ（Ｎ2)／Ｐ（Ａ
ｒ）ガス圧力比０．０２４以下のものの場合、合成され
た窒化ジルコニウムの量が少なかったために、格子定数
を求めることができなかった。Regarding the lattice constant, P (N 2 ) / P (A
r) In the case where the gas pressure ratio was 0.024 or less, the lattice constant could not be obtained because the amount of synthesized zirconium nitride was small.
【００２６】表１に見られる様に、生成相については試
料Ｎｏ．１［Ｐ（Ｎ2)／Ｐ（Ａｒ）比：０］では金属ジ
ルコニウムが合成され、試料Ｎｏ．２〜４［Ｐ（Ｎ2)／
Ｐ（Ａｒ）比：〜０．０２４］では金属ジルコニウムと
窒化ジルコニウムの混合相が合成された。一方試料Ｎ
ｏ．５〜９［Ｐ（Ｎ2)／Ｐ（Ａｒ）比：０．０２８以
上］では窒化ジルコニウムの単相が合成された。As can be seen from Table 1, regarding the produced phase, Sample No. In the case of the sample No. 1 [P (N 2 ) / P (Ar) ratio: 0], metallic zirconium was synthesized. 2 to 4 [P (N 2 ) /
A mixed phase of metallic zirconium and zirconium nitride was synthesized at a P (Ar) ratio of about 0.024]. On the other hand, sample N
o. In the case of 5 to 9 [P (N 2 ) / P (Ar) ratio: 0.028 or more], a single phase of zirconium nitride was synthesized.
【００２７】腐食速度は、試料Ｎｏ．４〜９ではいずれ
も０．０６ｍｍ／ｙ以下の小さな値を示したが、試料Ｎ
ｏ．４，５では不働態を示さず、不働態保持電流密度
は、１０００ｍＶ ｖｓ Ａｇ／ＡｇＣｌの電位で測定
した時夫々１０００μＡ／cm2,９００μＡ／cm2 と、大
きな値を示した。従ってこの電位においては皮膜の溶出
が著しくなっていることから、電極材料としての利用は
不適当であると考えられる。Corrosion rates are shown in Sample No. 4 to 9 all showed a small value of 0.06 mm / y or less.
o. No passive state was shown in Nos. 4 and 5, and the passive state holding current density showed large values of 1000 μA / cm 2 and 900 μA / cm 2 respectively when measured at a potential of 1000 mV vs Ag / AgCl. Therefore, the elution of the film is remarkable at this potential, and it is considered inappropriate to use it as an electrode material.
【００２８】試料Ｎｏ．６〜９では腐食速度が遅く、且
つ不働態保持電流密度が約１μＡ／cm2 と小さな値を示
していることから、１０００ｍＶ ｖｓ Ａｇ／ＡｇＣ
ｌの電位で使用しても十分な耐食性を示すことが分か
る。Sample No. In 6 to 9, the corrosion rate is slow and the passive state holding current density shows a small value of about 1 μA / cm 2 , so 1000 mV vs Ag / AgC.
It can be seen that sufficient corrosion resistance is exhibited even when used at a potential of 1.
【００２９】また密着性の評価において試料Ｎｏ．２〜
５は不良であったが、試料Ｎｏ．６〜９は良好な密着性
を示した。以上の結果から分る様にＰ（Ｎ2)／Ｐ（Ａ
ｒ）ガス圧力比０．０３５以上で作製した試料Ｎｏ．６
〜９の皮膜は良好な耐食性を示した。In the evaluation of adhesion, the sample No. 2 to
Although sample No. 5 was defective, sample no. 6-9 showed good adhesiveness. As can be seen from the above results, P (N 2 ) / P (A
r) Sample No. manufactured at a gas pressure ratio of 0.035 or more. 6
The coatings of -9 showed good corrosion resistance.
【００３０】この様に良好な耐食性を示す皮膜の格子定
数は４．６０Å以下となっており、言い換えれば４．６
０Å以下の格子定数を持つ窒化ジルコニウム皮膜が優れ
た耐食性を示すことが確認された。As described above, the film having good corrosion resistance has a lattice constant of 4.60 Å or less, in other words, 4.6.
It was confirmed that a zirconium nitride film having a lattice constant of 0Å or less exhibits excellent corrosion resistance.
【００３１】[0031]
【発明の効果】本発明に係る耐食性材料においては、皮
膜である窒化ジルコニウムの格子定数を４．６０Å以下
としたから、該皮膜自身の耐食性が改善され、優れた耐
食性を示す耐食性材料となる。INDUSTRIAL APPLICABILITY In the corrosion resistant material according to the present invention, the lattice constant of zirconium nitride, which is a film, is set to 4.60Å or less, so that the corrosion resistance of the film itself is improved and the corrosion resistant material exhibits excellent corrosion resistance.
【００３２】また耐食性材料の製造方法においては上記
の様にしたので、耐食性の優れた窒化ジルコニウム皮膜
を有する耐食性材料を製造することができる。従って本
発明により得られた耐食性材料は腐食性溶液中であって
も良好な防食性を示し、腐食環境下でのチャンバーとし
ての使用は勿論、電極用材料等の溶液中で電位をかけて
使用する部材としての適応が可能である。Further, since the method for producing a corrosion resistant material is as described above, it is possible to produce a corrosion resistant material having a zirconium nitride film excellent in corrosion resistance. Therefore, the corrosion-resistant material obtained by the present invention exhibits good corrosion resistance even in a corrosive solution, and can be used not only as a chamber in a corrosive environment but also by applying a potential in a solution such as an electrode material. It can be applied as a member that operates.
【図１】ＲＦマグネトロンスパッタリング装置を示す模
式図。FIG. 1 is a schematic diagram showing an RF magnetron sputtering apparatus.
１ ＲＦ電源 ２ 真空ポンプ ３ ジルコニウムターゲット ４ 基板 ５，６ 流量計 ７ 窒素ガスボンベ ８ アルゴンガスボンベ ９ ジルコニウム粒子 １０ アルゴン＋窒素プラズマ 1 RF Power Supply 2 Vacuum Pump 3 Zirconium Target 4 Substrate 5,6 Flowmeter 7 Nitrogen Gas Cylinder 8 Argon Gas Cylinder 9 Zirconium Particle 10 Argon + Nitrogen Plasma
Claims (3)
してなる耐食性材料において、 上記窒化ジルコニウムが格子定数４．６０Å以下のもの
であることを特徴とする腐食性溶液中で耐食性を示す耐
食性材料。1. A corrosion resistant material obtained by coating a surface of a base material with a zirconium nitride film, wherein the zirconium nitride has a lattice constant of 4.60 Å or less, and exhibits corrosion resistance in a corrosive solution. .
る耐食性材料を反応性スパッタリング法によって製造す
る方法において、 金属ジルコニウムをターゲットとし、 アルゴンガス分圧に対する窒素ガス分圧の比を０．０３
５以上として行なうことを特徴とする耐食性材料の製造
方法。2. A method for producing a corrosion resistant material having a zirconium nitride film on the surface of a substrate by a reactive sputtering method, wherein metal zirconium is used as a target, and the ratio of the partial pressure of nitrogen gas to the partial pressure of argon gas is 0.03.
A method for producing a corrosion resistant material, characterized in that it is carried out as 5 or more.
ス分圧の和を５×１０-2〜５×１０-4とし、 スパッタ時の基材温度を、セラミックス系基材では常温
〜１００℃とし、金属系基材では常温〜５００℃として
行う請求項２に記載の耐食性材料の製造方法。3. The sum of the argon gas partial pressure and the nitrogen gas partial pressure during sputtering is set to 5 × 10 −2 to 5 × 10 −4, and the substrate temperature during sputtering is room temperature to 100 ° C. for a ceramic-based substrate. The method for producing a corrosion resistant material according to claim 2, wherein the temperature of the metal-based substrate is from room temperature to 500 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32784893A JPH07180029A (en) | 1993-12-24 | 1993-12-24 | Corrosion resistant material and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32784893A JPH07180029A (en) | 1993-12-24 | 1993-12-24 | Corrosion resistant material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07180029A true JPH07180029A (en) | 1995-07-18 |
Family
ID=18203663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32784893A Withdrawn JPH07180029A (en) | 1993-12-24 | 1993-12-24 | Corrosion resistant material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07180029A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6485961B1 (en) * | 1996-12-05 | 2002-11-26 | Maxcyte, Inc. | Electrodes having a continuous, crystalline metal nitride coating and method of use |
| US6773669B1 (en) | 1995-03-10 | 2004-08-10 | Maxcyte, Inc. | Flow electroporation chamber and method |
| US7029916B2 (en) | 2001-02-21 | 2006-04-18 | Maxcyte, Inc. | Apparatus and method for flow electroporation of biological samples |
| US7141425B2 (en) | 2001-08-22 | 2006-11-28 | Maxcyte, Inc. | Apparatus and method for electroporation of biological samples |
| US7771984B2 (en) | 2004-05-12 | 2010-08-10 | Maxcyte, Inc. | Methods and devices related to a regulated flow electroporation chamber |
| CN106835042A (en) * | 2017-01-16 | 2017-06-13 | 厦门大学 | A kind of preparation method of transition metal nitride ultracapacitor coating material |
-
1993
- 1993-12-24 JP JP32784893A patent/JPH07180029A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6773669B1 (en) | 1995-03-10 | 2004-08-10 | Maxcyte, Inc. | Flow electroporation chamber and method |
| US6485961B1 (en) * | 1996-12-05 | 2002-11-26 | Maxcyte, Inc. | Electrodes having a continuous, crystalline metal nitride coating and method of use |
| US6617154B1 (en) * | 1996-12-05 | 2003-09-09 | Maxcyte, Inc. | Electroporation chamber including an electrode having a continuous, crystalline metal nitride coating |
| US7029916B2 (en) | 2001-02-21 | 2006-04-18 | Maxcyte, Inc. | Apparatus and method for flow electroporation of biological samples |
| US7141425B2 (en) | 2001-08-22 | 2006-11-28 | Maxcyte, Inc. | Apparatus and method for electroporation of biological samples |
| US7186559B2 (en) | 2001-08-22 | 2007-03-06 | Maxcyte, Inc. | Apparatus and method for electroporation of biological samples |
| US7771984B2 (en) | 2004-05-12 | 2010-08-10 | Maxcyte, Inc. | Methods and devices related to a regulated flow electroporation chamber |
| US9546350B2 (en) | 2004-05-12 | 2017-01-17 | Maxcyte, Inc. | Methods and devices related to a regulated flow electroporation chamber |
| CN106835042A (en) * | 2017-01-16 | 2017-06-13 | 厦门大学 | A kind of preparation method of transition metal nitride ultracapacitor coating material |
| CN106835042B (en) * | 2017-01-16 | 2019-02-22 | 厦门大学 | A kind of preparation method of transition metal nitride supercapacitor coating material |
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