JPS62199763A - Formation of tin film - Google Patents
Formation of tin filmInfo
- Publication number
- JPS62199763A JPS62199763A JP3964086A JP3964086A JPS62199763A JP S62199763 A JPS62199763 A JP S62199763A JP 3964086 A JP3964086 A JP 3964086A JP 3964086 A JP3964086 A JP 3964086A JP S62199763 A JPS62199763 A JP S62199763A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- tin film
- ion
- ion beam
- vacuum
- 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.)
- Granted
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 230000001133 acceleration Effects 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 9
- 238000010894 electron beam technology Methods 0.000 abstract description 4
- 230000001678 irradiating effect Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000009751 slip forming Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 22
- 239000000758 substrate Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000005566 electron beam evaporation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 241000269821 Scombridae Species 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
この発明は、耐蝕性に優れ、かつ、装飾性に優れたＴｉ
Ｎ膜を基材表面に形成する方法に関する〔背景技術〕
ＴｉＮは、高硬度で耐蝕性に優れ、かつ、特有の金色を
しているため、このＴｉＮの薄膜を基材表面に形成して
基材の硬度を上げたり、耐蝕性を付与したり、金色の装
飾を施したりすることが行われている。[Detailed Description of the Invention] [Technical Field] The present invention is directed to Ti, which has excellent corrosion resistance and decorative properties.
[Background technology] Regarding the method of forming a N film on the surface of a base material TiN has high hardness and excellent corrosion resistance, and has a unique golden color. Efforts are being made to increase the hardness of the material, add corrosion resistance, and add gold decorations.
基材上にＴｉＮ薄膜（０，１〜１０μｍ）を形成する方
法として、従来から、ＣＶＤ法あるいはＰＶＤ法（イオ
ンブレーティング、スパッタリング等）が用いられてい
る。Conventionally, a CVD method or a PVD method (ion blasting, sputtering, etc.) has been used to form a TiN thin film (0.1 to 10 μm) on a base material.
ところが、これらの方法には、つぎのような問題があっ
た。ｔなわち、ＣＶＤ法では基材温度を一般に１０００
℃程度の高温に加熱する必要があり、たとえば、鉄系の
合金板などを基材として用いた場合、基材が熱処理効果
によって変形してしまうという問題である。他方、ＰＶ
Ｄ法では、通常２００〜４００℃で処理されるので、基
材の変形といった問題はないが、ＨＣＤ （ホロカソー
ド）法、ＲＦ励起法、ＡＲＥ （活性化反応藤着）法な
どのイオンブレーティング法では、１０−２〜１０−’
Ｔｏｒｒの真空中で処理されるようになっており、真空
槽中の不純物ガス、槽壁の付着物、蒸発粒子の散乱等に
よって得られる膜の緻密性が損なわれ耐蝕性、密着性に
問題が生じる場合がある。さらに、基材にバイアス電圧
をかける必要があり、特に、連続処理を行う場合に設備
が複雑化する問題もある。スパッタリング法では、比較
的緻密な膜が得られるのであるが、生成速度が遅く、膜
の色が黒ずみやすい。色調調整にやはりバイアス電圧を
かけねばならなかった。However, these methods have the following problems. t, that is, in the CVD method, the substrate temperature is generally 1000
It is necessary to heat the material to a high temperature of approximately .degree. C., and when an iron-based alloy plate or the like is used as the base material, the problem is that the base material is deformed due to the heat treatment effect. On the other hand, P.V.
In method D, there is no problem of deformation of the base material because the treatment is usually carried out at 200 to 400°C, but ion blating methods such as HCD (holocathode) method, RF excitation method, and ARE (activated reaction fujicoat) method Then, 10-2 to 10-'
The process is carried out in a vacuum of Torr, and impurity gases in the vacuum chamber, deposits on the chamber wall, scattering of evaporated particles, etc. impair the density of the resulting film, causing problems in corrosion resistance and adhesion. may occur. Furthermore, it is necessary to apply a bias voltage to the base material, which poses the problem of complicating equipment, especially when performing continuous processing. Although a relatively dense film can be obtained using the sputtering method, the production rate is slow and the color of the film tends to darken. It was still necessary to apply a bias voltage to adjust the color tone.
この発明は、このような事情に鑑みて、基材上に耐蝕性
、耐摩耗性、密着性および装飾性に優れたＴｉＮを効率
よく得ることができるＴｉＮ膜の形成法を提供すること
を目的としている。In view of the above circumstances, an object of the present invention is to provide a method for forming a TiN film that can efficiently obtain TiN having excellent corrosion resistance, abrasion resistance, adhesion, and decorative properties on a substrate. It is said that
この発明らは、このような目的を達成するために、鋭意
検討した結果、イオンビーム法を用い真空中でＴｉを蒸
発させるとともに基材表面に比較的緩い加速電圧で窒素
イオンビームを照射すると、基材表面に耐蝕性、耐摩耗
性、密着性および装飾性に優れたＴｉＮを効率よく得る
ことができるということを見出し、この発明を完成する
に至った。In order to achieve such an objective, the present inventors conducted extensive research and found that by evaporating Ti in a vacuum using an ion beam method and irradiating the surface of the base material with a nitrogen ion beam at a relatively gentle acceleration voltage, The present inventors have discovered that it is possible to efficiently obtain TiN with excellent corrosion resistance, abrasion resistance, adhesion, and decorative properties on the surface of a substrate, and have completed the present invention.
したがって、この発明は、真空中に基材を配置して、Ｔ
ｉを蒸発させると同時に、前記基材表面に加速電圧Ｏ２
３〜２． ＯＫｅＶで窒素イオンビームを照射し、前記
基材表面にＴｉＮ膜を形成するＴｉＮ膜の形成法を要旨
とする。Therefore, this invention places the base material in vacuum and T
At the same time as evaporating i, an accelerating voltage O2 is applied to the surface of the base material.
3-2. The gist is a method for forming a TiN film, in which a TiN film is formed on the surface of the base material by irradiating a nitrogen ion beam with OKeV.
以下に、この発明を、その１実施例をあられす図面を参
照しつつ詳しく説明する。Hereinafter, one embodiment of the present invention will be described in detail with reference to the accompanying drawings.
第１図は、この発明にがかるＴｉＮ膜の形成を実施する
にあたり用いられるＴｉＮ膜形成装置をあられす。図に
みるように、このＴｉＮ膜形成装置は、真空槽（真空チ
ャンバー）１内にフープ状基板２が配置されるようにな
っている。このフープ状基材２は、矢印方向へ一定速度
で巻き取れるようになっている。基材２と対面する位置
には、電子ビーム蒸発源３が設けられている。この蒸発
源３には、金属チタン４が載せられ電子ビームによる加
熱によって蒸発させられるようになっている。真空槽１
壁面には、基材２に銃口を向けて２つのイオン銃５．６
が設けられている。一方のイオン銃５は、Ａｒ＋イオン
ビームを基板２に照射してボンバード処理を行うように
なっており、基材２の進行方向（図中、矢印方向）に対
して比較的後方の基材２表面に照準が合わせられている
。FIG. 1 shows a TiN film forming apparatus used for forming a TiN film according to the present invention. As shown in the figure, in this TiN film forming apparatus, a hoop-shaped substrate 2 is arranged in a vacuum chamber (vacuum chamber) 1. This hoop-shaped base material 2 can be wound up at a constant speed in the direction of the arrow. An electron beam evaporation source 3 is provided at a position facing the base material 2. Metal titanium 4 is placed on this evaporation source 3 and is evaporated by heating with an electron beam. Vacuum chamber 1
Two ion guns 5.6 are mounted on the wall with their muzzles facing the base material 2.
is provided. One ion gun 5 is configured to perform bombardment treatment by irradiating the substrate 2 with an Ar + ion beam, and is configured to irradiate the substrate 2 with an Ar + ion beam to perform bombardment processing, and is configured to irradiate the substrate 2 with an Ar + ion beam to perform bombardment. Aimed at the surface.
もう一方のイオン銃６は、一般に、窒素ガスをＮ２゛イ
オンビームとして基材２に照射するようになっており、
前述のイオン銃５より基板２の進行方向に対して前方の
基材２表面に照準が合わせられている。さらに、真空槽
ｌ内には、水晶振動子７ （レートセンサ）が前述のＡ
ｒ′″イオンビームおよびＮ２＋イオンビームが当たら
ない位置に設けられている。この水晶振動子７は、レー
トコントローラ（ＩＣ−６０００） ８との組み合わせ
によって金属チタンの蒸発量を制御するためのものであ
る。The other ion gun 6 is generally designed to irradiate the base material 2 with nitrogen gas as an N2 ion beam.
The above-mentioned ion gun 5 is aimed at the surface of the base material 2 in front of the substrate 2 in the traveling direction. Furthermore, in the vacuum chamber l, the crystal oscillator 7 (rate sensor) is installed as described above.
It is provided in a position where it is not hit by the r''' ion beam and the N2+ ion beam. This crystal oscillator 7 is used in combination with a rate controller (IC-6000) 8 to control the amount of evaporation of titanium metal. be.
図示していないが、このＴｉＮ膜形成装置には、真空槽
１内を真空にするための排気手段が設けられているのは
、言うまでもない。Although not shown, it goes without saying that this TiN film forming apparatus is provided with exhaust means for evacuating the inside of the vacuum chamber 1.
つぎに、この発明にかかるＴｉＮ膜の形成法を上記形成
装置を用いた場合を例にとって詳しく説明する。それは
、以下のようである。Next, a method for forming a TiN film according to the present invention will be explained in detail using the above-mentioned forming apparatus as an example. It is as follows.
■ 真空槽１内の所定位置にフープ状基材２をセントす
るとともに、電子ビーム蒸発源３上に金属チタン４を載
せる。(2) Place the hoop-shaped substrate 2 at a predetermined position in the vacuum chamber 1, and place the metal titanium 4 on the electron beam evaporation source 3.
■ 真空槽１内を排気手段で排気して１×１Ｏ−ＳＴｏ
ｒｒにする。■ Evacuate the inside of vacuum chamber 1 using an exhaust means to create 1×1O-STo.
Make it rr.
■ 基材２を一定速度で矢印方向に徐々に巻き取る。こ
れと同時に、Ａ ｒ＋イオンビームおよびＮ２゛イオン
ビームを加速電圧０．３〜２． ＯＫｅＶで基材２表面
へそれぞれのイオン銃５，６から照射する。■ Gradually wind up the base material 2 at a constant speed in the direction of the arrow. At the same time, the Ar+ ion beam and the N2'' ion beam are accelerated at a voltage of 0.3 to 2. The surface of the base material 2 is irradiated with OKeV from the respective ion guns 5 and 6.
この結果、蒸発した金属チタンは、たとえば、以下のよ
うな式、 。As a result, the evaporated titanium metal has the following formula, for example:
２Ｔｉ＋Ｎ、” ＋ｅ−−＋２ＴｉＮ
であられされるように、ＴｉＮに変化する。そして、イ
オンビームエネルギーによって密着性、緻密性、耐摩耗
性に優れるＴ’ｔＮ膜が基材２表面に連続的に形成され
る。ＴｉＮ膜時の基材の温度は、２００℃以下である。2Ti+N, "+e--+2TiN" and changes to TiN. Then, due to the ion beam energy, a T'tN film with excellent adhesion, denseness, and wear resistance is continuously formed on the surface of the base material 2. The temperature of the base material when forming the TiN film is 200° C. or lower.
膜は、蒸発源と基材間の距離、蒸発のパワー、イオンビ
ームのパワーを適切な値に設定することにより、１〜３
０人／Ｓの速度で成長させることができる。イオンビー
ムのパワーをあまり強くすると基材内に食い込んでしま
うので好ましくない。By setting the distance between the evaporation source and the substrate, the evaporation power, and the ion beam power to appropriate values, the film can
It can be grown at a rate of 0 people/S. It is not preferable to increase the power of the ion beam too much because it will dig into the base material.
つぎに、実施例を詳しく説明する。Next, examples will be explained in detail.
（実施例）
電子ビームパワー６ＫＶＸ ２００ｍＡの電子ビーム蒸
発源を基材からの距離３４０ｍｍに配置するとともに、
イオンビーム源としての０．５ＫｅＶ Ｘ ４０ｍＡの
イオン銃を基材がらの距離４５０１！ｌに配置した第１
図の装置を用い、基材としてのマルテンサイト系ステン
レス材表面にＴｉＮ膜を形成した。なお、基材の温度は
最高で８０℃であった。(Example) An electron beam evaporation source with an electron beam power of 6KVX 200mA was placed at a distance of 340mm from the base material, and
The distance from the base material to the 0.5KeV x 40mA ion gun as an ion beam source is 4501! The first placed in l
Using the apparatus shown in the figure, a TiN film was formed on the surface of a martensitic stainless steel material as a base material. Note that the temperature of the base material was 80° C. at maximum.
このようにして得たＴｉＮ膜形成基板と、従来の形成法
で得たＴｉＮ膜形成基板とを、それぞれ４０℃、３％Ｎ
ａＣ１水溶液に浸漬して放置したところ、実施例で得た
ＴｉＮ膜形成基板は、３日後でも異常が検出されなかっ
た。これに対し、従来の形成法で得たＴｉＮ膜形成基板
は、１日で鯖の発生が検出された。実施例で得たＴｉＮ
膜形成基板は、テープテストの結果でも密着性に異常が
なかった。さらに、ビッカース硬度は、２０００〜２５
００の高硬度であった。金色の色度調整も容易であった
。The TiN film-formed substrate obtained in this way and the TiN film-formed substrate obtained by the conventional forming method were heated at 40°C with 3% N
When the TiN film-formed substrate obtained in the example was immersed in the aC1 aqueous solution and left to stand, no abnormality was detected even after 3 days. On the other hand, on the TiN film-formed substrate obtained by the conventional formation method, the occurrence of mackerel was detected within one day. TiN obtained in Example
The tape test results showed no abnormality in adhesion of the film-formed substrate. Furthermore, Vickers hardness is 2000-25
It had a high hardness of 0.00. It was also easy to adjust the chromaticity of gold.
この発明にがかるＴｉＮ膜の形成法は、上記実施例に限
定されない。たとえば、連続処理でなくバッチ処理でも
構わない。バッチ処理の場合、イオン銃を１つにして、
ガスの切り換えによってＡｒ゛イオンビームおよびＮ２
１イオンビームを基材表面へそれぞれ照射するようにし
ても構わない。基材も板状に限らない。ボンバード処理
にもちいられるガスは、Ａｒなどの希ガス類に限らすＮ
２などでも構わない。The method for forming a TiN film according to the present invention is not limited to the above embodiment. For example, batch processing may be used instead of continuous processing. For batch processing, use one ion gun,
By switching the gas, Ar゛ ion beam and N2
One ion beam may be applied to each base material surface. The base material is not limited to a plate shape either. The gases used for the bombardment process are limited to rare gases such as Ar and N.
2 etc. is fine.
この発明のＴｉＮ膜の形成法は、以上のように、真空中
に基材を配置して、’ｒｔを論発させると同時に、前記
基材表面に加速電圧０．３〜２．０ Ｋｅνで窒素イオ
ンビームを照射し、前記基材表面にＴｉＮ膜を形成する
ようになっているので、従来より、高真空側で処理でき
、Ｎ、ガス量が少な（すみ、かつ、基材にバイアス電圧
をかける必要がなく、連続処理の場合も、装置が複雑に
ならない。As described above, the method for forming a TiN film of the present invention involves placing a base material in a vacuum, developing 'rt, and at the same time applying an accelerating voltage of 0.3 to 2.0 Keν to the surface of the base material. Since a TiN film is formed on the surface of the base material by irradiation with a nitrogen ion beam, the process can be performed in a higher vacuum than before, and the amount of N and gas is small (and the bias voltage is not applied to the base material). There is no need to apply pressure, and even in the case of continuous processing, the equipment does not become complicated.
したがって、基材上に耐蝕性、密着性および装飾性に優
れたＴｉＮ膜を効率よく、かつ、安価で得ることができ
る。Therefore, a TiN film with excellent corrosion resistance, adhesion and decorative properties can be efficiently and inexpensively obtained on a substrate.
第１図はこの発明にがかるＴｉＮ膜の形成法を実施する
にあたり用いられるＴ ｉ Ｎ膜形成装置の１実施例を
説明する概略説明図である。
１・・・真空槽 ２・・・フープ状基材 ３・・・電、
子ビーム蒸発源 ４・・・金属チタン ５．６・・・イ
オン銃代理人 弁理士 松 本 武 彦
第１ 図FIG. 1 is a schematic explanatory diagram illustrating one embodiment of a TiN film forming apparatus used to carry out the TiN film forming method according to the present invention. 1... Vacuum chamber 2... Hoop-shaped base material 3... Electricity,
Child beam evaporation source 4...Metal titanium 5.6...Ion gun agent Patent attorney Takehiko Matsumoto Figure 1
Claims (1)
時に、前記基材表面に加速電圧０．３〜２．０ＫｅＶで
窒素イオンビームを照射し、前記基材表面にＴｉＮ膜を
形成するＴｉＮ膜の形成法。(1) A base material is placed in a vacuum, and while Ti is evaporated, the surface of the base material is irradiated with a nitrogen ion beam at an acceleration voltage of 0.3 to 2.0 KeV to form a TiN film on the surface of the base material. A method for forming a TiN film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3964086A JPS62199763A (en) | 1986-02-25 | 1986-02-25 | Formation of tin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3964086A JPS62199763A (en) | 1986-02-25 | 1986-02-25 | Formation of tin film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1236361A Division JPH0686657B2 (en) | 1989-09-11 | 1989-09-11 | Thin film forming equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62199763A true JPS62199763A (en) | 1987-09-03 |
| JPH0551661B2 JPH0551661B2 (en) | 1993-08-03 |
Family
ID=12558688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3964086A Granted JPS62199763A (en) | 1986-02-25 | 1986-02-25 | Formation of tin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62199763A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215966A (en) * | 1988-02-23 | 1989-08-29 | Nissin Electric Co Ltd | Manufacture of high-hardness tin film |
| JPH03177570A (en) * | 1989-12-05 | 1991-08-01 | Raimuzu:Kk | Production of combined hard material |
| CN111893439A (en) * | 2020-08-11 | 2020-11-06 | 苏州众智泽智能科技有限公司 | Method for preparing personal ornaments with titanium nitride hard coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58181864A (en) * | 1982-04-16 | 1983-10-24 | Sumitomo Electric Ind Ltd | Surface treatment method |
| JPS6115967A (en) * | 1984-06-29 | 1986-01-24 | Sumitomo Electric Ind Ltd | Surface treatment |
| JPS61195971A (en) * | 1985-02-25 | 1986-08-30 | Kobe Steel Ltd | Formation of wear resisting film |
-
1986
- 1986-02-25 JP JP3964086A patent/JPS62199763A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58181864A (en) * | 1982-04-16 | 1983-10-24 | Sumitomo Electric Ind Ltd | Surface treatment method |
| JPS6115967A (en) * | 1984-06-29 | 1986-01-24 | Sumitomo Electric Ind Ltd | Surface treatment |
| JPS61195971A (en) * | 1985-02-25 | 1986-08-30 | Kobe Steel Ltd | Formation of wear resisting film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215966A (en) * | 1988-02-23 | 1989-08-29 | Nissin Electric Co Ltd | Manufacture of high-hardness tin film |
| JPH03177570A (en) * | 1989-12-05 | 1991-08-01 | Raimuzu:Kk | Production of combined hard material |
| CN111893439A (en) * | 2020-08-11 | 2020-11-06 | 苏州众智泽智能科技有限公司 | Method for preparing personal ornaments with titanium nitride hard coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0551661B2 (en) | 1993-08-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |