JPH0466667A - Formation of titanium nitride film and cooking pots and pans - Google Patents
Formation of titanium nitride film and cooking pots and pansInfo
- Publication number
- JPH0466667A JPH0466667A JP17696890A JP17696890A JPH0466667A JP H0466667 A JPH0466667 A JP H0466667A JP 17696890 A JP17696890 A JP 17696890A JP 17696890 A JP17696890 A JP 17696890A JP H0466667 A JPH0466667 A JP H0466667A
- Authority
- JP
- Japan
- Prior art keywords
- titanium nitride
- film
- nitride film
- frying pan
- nitrogen
- 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
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000010411 cooking Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 16
- 230000006641 stabilisation Effects 0.000 claims description 11
- 238000011105 stabilization Methods 0.000 claims description 11
- 239000010408 film Substances 0.000 claims 11
- 239000010409 thin film Substances 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 77
- 239000010936 titanium Substances 0.000 abstract description 27
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010931 gold Substances 0.000 abstract description 7
- 229910052737 gold Inorganic materials 0.000 abstract description 7
- 238000002845 discoloration Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 150000002926 oxygen Chemical class 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 25
- 239000002585 base Substances 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 12
- 238000005498 polishing Methods 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000467686 Eschscholzia lobbii Species 0.000 description 2
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Frying-Pans Or Fryers (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
この発明は、基体表面に窒化チタン（以下、ＴｉＮと略
す）被膜を形成する方法に係わり、特に加熱による色調
変化のないＴｉＮ被膜の形成方法及びその形成方法によ
り得られたＴｉＮ被膜を有する調理用鍋類に関する。Detailed Description of the Invention "Industrial Application Field" The present invention relates to a method for forming a titanium nitride (hereinafter abbreviated as TiN) film on the surface of a substrate, and in particular a method for forming a TiN film that does not change color tone due to heating. The present invention also relates to cooking pots having a TiN coating obtained by the method for forming the same.
「従来の技術」
従来、ネクタイピン、腕時計のフレーム等では、その表
面にＴｉＮ被膜を形成することにより、装飾性のある高
級感を付与するとともに耐蝕性及び耐摩耗性などを向上
させるＴｉＮコーティングが行われてきている。``Prior Art'' Conventionally, tie pins, watch frames, etc., have been coated with TiN coating to give them a decorative and luxurious look and to improve their corrosion and abrasion resistance. It's been done.
このＴｉＮ被膜は美しい金色を呈し、耐蝕性や耐摩耗性
も良好なことから、優れたコーテイング材として上記装
飾品類のほか、刃物等の表面処理にも用いられつつある
。This TiN coating has a beautiful golden color and has good corrosion resistance and abrasion resistance, so it is being used as an excellent coating material not only for the above-mentioned decorative items but also for surface treatment of cutlery and the like.
このＴｉＮ被膜は、上記のネクタイピンや腕時計のフレ
ーム等の装飾品類のように、通常常温で使用される物品
にあっては、その美しい色調が半永久的に維持される。This TiN coating maintains its beautiful color tone semi-permanently in articles that are normally used at room temperature, such as the above-mentioned decorative items such as tie clips and watch frames.
「発明が解決しようとする課題」
しかしながら、調理用鍋類のように、空気中で数百度の
温度に加熱される物品では、表面に形成したＴｉＮ被膜
が加熱によって変色し、美しい金色がくすんだ色になっ
てしまう問題があった。``Problems to be Solved by the Invention'' However, for items such as cooking pots that are heated to temperatures of several hundred degrees in the air, the TiN coating formed on the surface changes color due to heating, and the beautiful golden color becomes dull. There was a problem with the color changing.
この変色は、ＴｉＮ被膜を大気中で加熱すると３００℃
付近から始まり、最終的には金色が暗黄色から赤黄色に
変色してしまう。その原因は、真空中（１ｘ ｌ ０−
５Ｔｏｒｒ）加熱では変色が生じないことや、変色した
ＴｉＮ被膜中からＴｉｅ、が検出されることなどから、
被膜中に残存する未反応のＴｉと酸素との反応に起因し
た過剰なＴｉｄｙの形成によるものと考えられる。また
ＴｉＮ被膜を大気中で加熱することによる色調変化の度
合は、このＴ ｉｏ を生成膜の厚さに大きく依存して
いるものと推測される。（ただし、膜厚数１００人程程
度Ｔ ｉ Ｏを被膜は透明である。）
本発明は上記事情に鑑みてなされたしので、ＴｉＮ被膜
が高温条件下に置かれても色調の安定を保持することが
可能となるＴｉＮ被膜の形成方法、及びその方法により
得られたＴｉＮ被膜を有する調理用鍋類を提供すること
を目的とする。This discoloration occurs when the TiN film is heated to 300°C in the air.
It starts in the vicinity and eventually the gold color changes from dark yellow to reddish-yellow. The reason is that in vacuum (1x l 0-
5Torr) heating does not cause discoloration, and Tie is detected in the discolored TiN film.
This is thought to be due to the formation of excessive Tidy due to the reaction between unreacted Ti remaining in the film and oxygen. Furthermore, it is presumed that the degree of color tone change caused by heating the TiN film in the atmosphere is largely dependent on the thickness of the formed film. (However, the TiN coating is transparent, with a thickness of about 100 layers.) The present invention was made in view of the above circumstances, so that the TiN coating maintains color stability even when placed under high temperature conditions. It is an object of the present invention to provide a method for forming a TiN film that enables the formation of a TiN film, and cooking pots having a TiN film obtained by the method.
「課題を解決するための手段」
かかる課題は、請求項１に記載したように基体表面に窒
化チタン被膜を成膜した後、この基体を酸素と窒素混合
雰囲気中で加熱し、窒化チタン被膜表面に厚さ数１００
Ａの極めて薄層の酸化チタン被膜を形成することによる
色調安定化処理を行うことにより解消される。"Means for Solving the Problem" This problem is solved by forming a titanium nitride film on the surface of a substrate as described in claim 1, and then heating the substrate in a mixed atmosphere of oxygen and nitrogen. thickness number 100
This problem can be solved by carrying out the color tone stabilization treatment by forming an extremely thin titanium oxide film (A).
すなわち、薄層のＴｉ０ｚ被膜は透明であることがらＴ
ｉＮ被膜の金色の色調を変えることなく、かつ大気中の
酸素の侵入をＴ ｉ Ｏを被膜により抑制する働きを有
する。That is, since the thin Ti0z film is transparent, T
It has the function of suppressing the intrusion of oxygen from the atmosphere by using the T i O film without changing the golden color tone of the iN film.
また、請求項２に記載した発明は．鍋基体表面に窒化チ
タン被膜を成膜し、これを酸素と窒素の混合雰囲気中で
加熱し、窒化チタン被膜表面に酸化チタン薄層を形成さ
け色調を安定化させた調理用鍋類である。Moreover, the invention described in claim 2 is... These cooking pots are made by forming a titanium nitride film on the surface of the pot base and heating it in a mixed atmosphere of oxygen and nitrogen to form a thin layer of titanium oxide on the surface of the titanium nitride film to stabilize the color tone.
また上記課題は、請求項３に記載したように基体表面に
窒化チタン被膜を成膜した後、この基体を窒素雰囲気中
で加熱し、窒化チタン被膜中に窒素を拡散させ、残存す
るチタンを窒化チタンとして固定することによる色調安
定化処理を行うことにより解消される。Further, the above problem is solved by forming a titanium nitride film on the surface of a substrate, heating the substrate in a nitrogen atmosphere, diffusing nitrogen into the titanium nitride film, and nitriding the remaining titanium. This can be resolved by performing a color tone stabilization treatment by fixing it as titanium.
また、請求項４に記載した発明は．鍋基体表面に窒化チ
タン被膜を成膜した後、これを窒素雰囲気中で加熱し、
窒化チタン被膜中に窒素を拡散させ、残存するチタンを
窒化チタンとして固定し、色調を安定化させた調理用鍋
類である。Moreover, the invention described in claim 4 is... After forming a titanium nitride film on the surface of the pot base, this is heated in a nitrogen atmosphere,
These cooking pots have a stabilized color tone by diffusing nitrogen into the titanium nitride coating and fixing the remaining titanium as titanium nitride.
「作用」
基体表面に窒化チタン被膜を成膜した後、この基体を酸
素と窒素の混合雰囲気中、あるいは窒素単独雰囲気中で
加熱を行い、窒化チタン被膜中に酸素あるいは窒素を拡
散させて、ＴｉＮ被膜中に残存するＴｉと酸素あるいは
窒素を反応させることにより、高温時における色調の安
定性に優れたＴｉＮ被膜が得られる。"Operation" After forming a titanium nitride film on the surface of the substrate, this substrate is heated in a mixed atmosphere of oxygen and nitrogen or in an atmosphere of nitrogen alone to diffuse oxygen or nitrogen into the titanium nitride film, forming a TiN By reacting Ti remaining in the film with oxygen or nitrogen, a TiN film with excellent color stability at high temperatures can be obtained.
以下、図面を参照して本発明の詳細な説明する。Hereinafter, the present invention will be described in detail with reference to the drawings.
第１図は、本発明に係るＴｉＮ被膜の形成方法の一例と
して、フライパン（基体）表面にＴｉＮ被膜を形成する
方法を説明するための図である。この図中符号１はフラ
イパン基体、２はＴｉＮ被膜を形成したフライパン、３
は色調安定化処理をしたフライパン、４は研磨洗浄装置
、５はイオンブレーティング装置、６は色調安定化処理
工程を行うための熱処理装置である。FIG. 1 is a diagram for explaining a method of forming a TiN film on the surface of a frying pan (substrate) as an example of the method of forming a TiN film according to the present invention. In this figure, 1 is a frying pan base, 2 is a frying pan with a TiN coating formed thereon, and 3 is a frying pan base.
Reference numeral 4 indicates a frying pan subjected to color stabilization treatment, 4 is a polishing cleaning device, 5 is an ion blating device, and 6 is a heat treatment device for carrying out the color tone stabilization treatment step.
この装置によりフライパン基体１表面にＴｉＮ被膜を形
成するには、まず研磨洗浄装置４によりフライパン基体
１表面を研磨及び清浄化する。In order to form a TiN film on the surface of the frying pan base 1 using this device, first, the surface of the frying pan base 1 is polished and cleaned using the polishing and cleaning device 4 .
このフライパン基体１は、鋼などの金属材料からなるも
のである。このフライパン基体ｌは、その成型工程にお
いてＴｉＮ被膜の基板に対する付着力低下の原因となる
被成膜表面の凹凸、あるいはダストや油脂の付着の恐れ
があるため、研磨洗浄装置４内でその表面を研磨し、さ
らに純水、酸、アルカリ等により脱脂洗浄する。このよ
うにして表面の耐処理を受けたフライパン基体１は、次
にイオンブレーティング装置５により、その表面にＴｉ
Ｎ被膜を成膜する。このイオンブレーティング装置５は
、第２図に示すように装置本体５Ａと、被膜材料のチタ
ン７を入れるるつぼ８と、基板電源９と、ガス（Ａｒ、
Ｎｔ）供給調節装置１０と、イオン化電極１１と、電子
ビーム装置１２と、真空装置１３と、ヒーター１４と、
ガス（Ａｒ、Ｎｔ）供給口１５を備えて構成されている
。This frying pan base 1 is made of a metal material such as steel. The surface of the frying pan base 1 is cleaned in the polishing and cleaning device 4 to prevent unevenness on the surface of the film to be formed, or the adhesion of dust and oil, which may cause a decrease in the adhesion of the TiN film to the substrate during the molding process. Polish and then degrease and clean with pure water, acid, alkali, etc. The frying pan base 1 whose surface has been subjected to the surface treatment in this way is then treated with Ti on its surface by the ion blating device 5.
A N film is formed. As shown in FIG. 2, this ion blating apparatus 5 includes an apparatus main body 5A, a crucible 8 containing titanium 7 as a coating material, a substrate power source 9, and gases (Ar,
Nt) supply adjustment device 10, ionization electrode 11, electron beam device 12, vacuum device 13, heater 14,
It is configured to include a gas (Ar, Nt) supply port 15.
フライパン基体ｌは、チタン７の入ったるつぼ８と対向
する側に配置され、基板電源９により、数百ボルトの電
圧が印加されている。イオンブレーティング装置本体５
Ａ内は、真空装置１３により圧力１０−５〜１０−’Ｔ
ｏｒｒ程度の真空状態としておく。このような条件下
において、ガス供給調節装置ＩＯにより装置内にＡｒガ
スを吹き込み、Ａｒ雰囲気でフライパン基体ｌの表面を
イオンボンバードし、さらに電子ビーム装置１２によっ
て、るつぼ８に設置しておいたチタン７を加熱蒸散させ
てＴｉ粒子とし、そのＴｉ粒子をイオン化電極１１でイ
オン化してフライパン基体１表面に衝突させ、Ｔｉ被膜
を形成する。このＴｉ被膜の厚さが数百人の膜厚になっ
た時点でフライパン基体Ｉの印加電圧を下げ、イオンブ
レーティング装置本体５Ａ内にガス供給口１５からＮ、
ガスを導入する。The frying pan base 1 is placed on the side facing the crucible 8 containing the titanium 7, and a voltage of several hundred volts is applied by a substrate power supply 9. Ion brating device main body 5
Inside A, the pressure is 10-5 to 10-'T by the vacuum device 13.
A vacuum state of about orr is maintained. Under these conditions, Ar gas is blown into the device by the gas supply adjustment device IO, the surface of the frying pan base l is ion bombarded in an Ar atmosphere, and the titanium placed in the crucible 8 is ion-bombarded by the electron beam device 12. 7 is heated and evaporated to form Ti particles, which are ionized by an ionizing electrode 11 and collided with the surface of the frying pan base 1 to form a Ti film. When the thickness of this Ti coating reaches several hundred layers, the voltage applied to the frying pan base I is lowered, and the gas supply port 15 is connected to the N,
Introduce gas.
このときのイオンブレーティング装置５内圧は、１０−
５Ｔｏｒｒ程度となるようにガス（Ａｒ、Ｎｔ）供給調
節装置１０て調節する。このようにして前述のイオン化
したＴｉ粒子と、同様にイオン化電極１１によりイオン
化されたＮ、ガスとを反応させて、フライパン基体１表
面のＴｉ被膜の上に、膜厚２〜３μｌのＴｉＮ被膜を形
成してフライパン２となる。次に、このフライパン２を
熱処理装置６内に入れる。この熱処理装置６は第３図に
示すように、処理装置本体６Ａと、窒素（Ｎ、）ガスボ
ンベ１６と、酸素（０，）ガスボンベ１７と、純化器１
８．１９と、ヒーター２０と、棚２１と、ポンプ２２を
備えて構成されている。この熱処理装置本体６Ａ内の棚
２１にＴｉＮ形成フライパン２を設置してこれを加熱す
る。このときＮ、ガスボンベ１６及びＯ，ガスボンベ１
７からは、それぞれ純化器１８．１９を経てＮ、ガス、
０．ガスを熱処理装置本体６Ａ内に送り出して、熱処理
装置本体６Ａ内をＯｆ／Ｎ！−１／２０〜Ｉ１５の雰囲
気に保っておく。The internal pressure of the ion brating device 5 at this time is 10-
The gas (Ar, Nt) supply adjustment device 10 is used to adjust the pressure to about 5 Torr. In this way, the ionized Ti particles described above are reacted with N and gas similarly ionized by the ionization electrode 11 to form a TiN coating with a thickness of 2 to 3 μl on the Ti coating on the surface of the frying pan base 1. Form into frying pan 2. Next, this frying pan 2 is placed into a heat treatment device 6. As shown in FIG. 3, this heat treatment apparatus 6 includes a treatment apparatus main body 6A, a nitrogen (N,) gas cylinder 16, an oxygen (0,) gas cylinder 17, and a purifier 1.
8.19, a heater 20, a shelf 21, and a pump 22. A TiN forming frying pan 2 is installed on a shelf 21 in the heat treatment apparatus main body 6A and heated. At this time, N, gas cylinder 16 and O, gas cylinder 1
From 7, N, gas,
0. Gas is sent into the heat treatment apparatus main body 6A, and the inside of the heat treatment apparatus main body 6A is turned off/on! - Maintain an atmosphere of 1/20 to I15.
上記条件で、ヒーター２０によりＴｉＮ形成フライパン
２を３５０〜５００℃に加熱し、これによってＴｉＮ被
膜表面に均一な数１００人程程度膜厚のＴ ｉ Ｏを被
膜を形成させることにより、色調が安定化したＴｉＮ被
膜をもつフライパン３が得られる。Under the above conditions, the TiN forming frying pan 2 is heated to 350 to 500°C using the heater 20, thereby forming a uniform TiO film on the surface of the TiN film with a thickness of about several hundred layers, thereby stabilizing the color tone. A frying pan 3 having a TiN film obtained is obtained.
ここで、この操作における温度条件（３５０〜５００°
Ｃ）は、フライパンを高温で使用する際の上限付近の温
度でかつＴｉＮの色調である金色を失わない温度に設定
される。Here, the temperature conditions for this operation (350 to 500°
C) is set at a temperature near the upper limit when the frying pan is used at high temperatures and at a temperature that does not lose the golden color tone of TiN.
また、このＴｉＮ被膜の形成方法においては、イオンブ
レーティング法によりＴｉＮ被膜を形成する際にＴｉ／
Ｎの組成割合を変えることにより、熱処理後のＴｉＮ被
膜を様々な色調にすることができる。例えば、本例にお
けるイオンブレーティング装置の条件をＴｉ／Ｎ＝２．
０前後とすればＴｉＮ成膜時は薄金色て熱処理後は金色
となり、Ｔｉ／Ｎ＝１．０前後とすればＴｉＮ成膜時は
金色で、熱処理後は濃金色となるＴｉＮ被膜を形成した
色調安定化フライパンが得られる。In addition, in this method of forming a TiN film, Ti/
By changing the composition ratio of N, the TiN film after heat treatment can be made into various colors. For example, the conditions of the ion blating apparatus in this example are Ti/N=2.
If it was around 0, a TiN film was formed that was light gold in color and became gold after heat treatment, and if Ti/N was around 1.0, a TiN film was formed that was gold in color when TiN was formed and became dark gold after heat treatment. A color stabilized frying pan is obtained.
以上のようにして、フライパン基体１表面には高温条件
における色調安定性に優れたＴｉＮ被膜２９が形成され
、第５図に示すようなフライパン３が得られる。As described above, a TiN coating 29 having excellent color stability under high temperature conditions is formed on the surface of the frying pan base 1, and a frying pan 3 as shown in FIG. 5 is obtained.
このＴｉＮ被膜の形成方法によれば、ＴｉＮ被膜中のＴ
ｉを酸素と窒素の混合雰囲気中で加熱してＴｉＮ表面に
極めて薄層のＴ ｉＯを被膜を形成させることによりＴ
ｉＮ被膜の色調を加熱に対し安定化させることができる
。また、イオンブレーティング装置で成膜する際の条件
のうち、Ｔｉ／Ｎの割合を適宜に調節することにより、
種々の色調のＴｉＮ被膜を形成することができる。According to this method of forming a TiN film, T in the TiN film is
T by heating i in a mixed atmosphere of oxygen and nitrogen to form an extremely thin layer of TiO on the TiN surface.
The color tone of the iN film can be stabilized against heating. In addition, by appropriately adjusting the Ti/N ratio among the conditions when forming a film with an ion blating device,
TiN coatings of various colors can be formed.
また先の方法により得られたフライパンは、その表面に
美しい金色の色調をもつＴｉＮ被膜を形成したものなの
でフライパンの装飾性が向上し、高級感を付与できる。Furthermore, since the frying pan obtained by the above method has a TiN coating with a beautiful golden color formed on its surface, the decorativeness of the frying pan is improved and a sense of luxury can be imparted to the frying pan.
またこのＴｉＮ被膜は色調安定化処理されているので、
調理時に加熱しても変色することがなく、美しい金色の
色調が長期間維持される。In addition, this TiN coating has been subjected to color stabilization treatment, so
It does not discolor even when heated during cooking, and maintains its beautiful golden color for a long time.
次に本発明に係るＴｉＮ被膜形成方法の他の例を説明す
る。Next, another example of the TiN film forming method according to the present invention will be explained.
この例では先の例と同様の装置を用い、かつ同様の操作
によりフライパン基体１表面にＴｉＮ被膜を形成しフラ
イパン２を得る。そして得られたフライパン２を、第４
図に示す熱処理装置２３内に設置する。In this example, a TiN film is formed on the surface of the frying pan base 1 by using the same apparatus as in the previous example and performing the same operations to obtain the frying pan 2. Then, put the obtained frying pan 2 into the fourth frying pan.
It is installed in the heat treatment apparatus 23 shown in the figure.
この熱処理装置２３は処理装置本体２３Ａと、窒素（Ｎ
、）ガスボンベ２４と、純化器２５と、ヒーター２６と
、棚２７と、ポンプ２Ｂを備えて構成されている。This heat treatment device 23 includes a treatment device main body 23A and nitrogen (N
,) It is configured to include a gas cylinder 24, a purifier 25, a heater 26, a shelf 27, and a pump 2B.
フライパン２は棚２７に設置され、Ｎ、ガスボンベ２４
からＮ、ガスを純化器２５を経て熱処理装置本体２３Ａ
内に送り込む。このようにして熱処理装置本体２３Ａ内
はＮ、雰囲気（７６０〜７６５Ｔｏｒｒ）に保たれ、さ
らにこの条件でヒーター２６によりフライパン２を３５
０〜６００℃に加熱することにより、ＴｉＮ被膜中に窒
素が拡散して成膜時に残存していたＴｉがＴｉＮとなる
。このときＴｉＮ被膜中に残存するＴｉのうち上記温度
条件でＮ、と反応可能なＴｉの殆どは反応してＴｉＮと
なり、その後上述の温度（３５０〜６００℃）より低い
温度で加熱してもＴｉＮ被膜中には既に大気中の酸素に
より酸化されるべきＴｉが存在しないため、ＴｉＮ被膜
の色調変化は起こらない。The frying pan 2 is installed on the shelf 27, and the N gas cylinder 24
From there, the N gas is passed through the purifier 25 to the heat treatment equipment main body 23A.
send it inside. In this way, the interior of the heat treatment apparatus main body 23A is maintained at a N atmosphere (760 to 765 Torr), and further, under this condition, the frying pan 2 is heated to 35°C by the heater 26.
By heating to 0 to 600°C, nitrogen diffuses into the TiN film, and the Ti remaining during film formation becomes TiN. At this time, of the Ti remaining in the TiN film, most of the Ti that can react with N under the above temperature conditions reacts to become TiN. Since there is already no Ti in the coating to be oxidized by oxygen in the atmosphere, no change in color tone of the TiN coating occurs.
以上のようにして、フライパン基体１表面上には高温条
件における色調安定性に優れたＴｉＮ被膜が形成され、
色調安定化フライパンが得られる。As described above, a TiN film with excellent color stability under high temperature conditions is formed on the surface of the frying pan base 1,
A color stabilized frying pan is obtained.
このＴｉＮ被膜の形成方法によれば、ＴｉＮ被膜中に残
存しているＴｉを窒素の単独雰囲気中で加熱してＴｉＮ
とすることにより、ＴｉＮ被膜の色調を安定化させるこ
とができる。また色調安定化処理によりＴｉＮ被膜中に
残存するＴｉの殆どがＴｉＮになっているため、色調安
定化処理前のＴｉＮ被膜に比べ、より純金に近い優れた
色調のＴｉＮ被膜が得られる。According to this method of forming a TiN film, Ti remaining in the TiN film is heated in a nitrogen atmosphere alone to form a TiN film.
By doing so, the color tone of the TiN film can be stabilized. Moreover, since most of the Ti remaining in the TiN coating is changed to TiN by the color stabilization treatment, a TiN coating with an excellent color tone closer to that of pure gold can be obtained compared to the TiN coating before the color tone stabilization treatment.
なお上記各側においては、イオンブレーティング法を用
いてＴｉＮ被膜を形成しているが、その他の成膜方法、
例えばスパッタ法や蒸着法あるいは化学蒸着法等を用い
てＴｉＮ被膜を形成してもよい。Although the TiN film is formed on each of the above sides using the ion blating method, other film forming methods,
For example, the TiN film may be formed using a sputtering method, a vapor deposition method, a chemical vapor deposition method, or the like.
また上記各側においては、本発明の方法をフライパンに
適用しているが、フライパン以外の比較的底の浅い調理
用ＭｔＭや調理用のへら等の様々な加熱調理用品への適
用も可能である。Furthermore, in each of the above aspects, the method of the present invention is applied to a frying pan, but it can also be applied to various heating cooking utensils other than a frying pan, such as a relatively shallow cooking MtM and a cooking spatula. .
「実施例」
第１図ないし第４図に示す装置を用いて、表面に色調安
定化処理ＴｉＮ被膜を有するフライパンを作製した。"Example" Using the apparatus shown in FIGS. 1 to 4, a frying pan having a color-stabilized TiN coating on its surface was produced.
まずスチール族のフライパン基体１を研磨洗浄装置４内
に入れ、表面研磨の後、水洗浄、純水洗浄、酸洗浄、ア
ルカリ洗浄、再水洗浄、アルコール洗浄と順次洗浄した
。First, a steel frying pan substrate 1 was placed in a polishing and cleaning device 4, and after surface polishing, it was sequentially cleaned with water cleaning, pure water cleaning, acid cleaning, alkali cleaning, rewater cleaning, and alcohol cleaning.
研磨洗浄装置４内で研磨洗浄したフライパン基体１を、
さらにイオンブレーティング装置本体５Ａ内に取り付け
た。イオンブレーティング装置本体５Ａ内は、真空装置
１３により圧力ｌ０−５〜１０−’Ｔｏｒｒ程度の真空
状態にしておき、取り付けたフライパン基体１に数１０
０ボルトの電圧を印加した。次いで装置内にＡｒガスを
吹き込み、Ａｒ雰囲気でフライパン基体１表面をイオン
ボンバードし、さらに膜厚２００オングストロームのＴ
ｉ層をフライパン基体１表面に成膜した。次にフライパ
ン基体１の印加電圧を下げ、イオンブレーティング装置
本体５Ａ内にガス供給調節装Ｒ１０によりＴｉ／Ｎ＝１
．０となるようにＮ、ガスを入れ、イオンブレーティン
グ装置本体５Ａ内圧を１０−５Ｔｏｒｒ程度とし、膜厚
２〜３１．ｔ ｘのＴｉＮ層を形成した。The frying pan base 1 polished and cleaned in the polishing cleaning device 4,
Furthermore, it was installed inside the ion brating device main body 5A. The inside of the ion brating device main body 5A is kept in a vacuum state with a pressure of about 10-5 to 10-' Torr by the vacuum device 13, and several tens of
A voltage of 0 volts was applied. Next, Ar gas was blown into the device to ion bombard the surface of the frying pan base 1 in an Ar atmosphere, and then a T film with a thickness of 200 angstroms was applied.
An i-layer was formed on the surface of the frying pan base 1. Next, the voltage applied to the frying pan base 1 is lowered, and the gas supply adjustment device R10 is adjusted to Ti/N=1 in the ion blating device main body 5A.
．． 0, and the internal pressure of the ion blating device main body 5A is set to about 10-5 Torr, and the film thickness is 2 to 31 Torr. A TiN layer of tx was formed.
上記方法により、得たフライパン２を熱処理装置本体６
Ａ内の棚に設置し、Ｎ、ガスボンベ１６及び０．ガスボ
ンベ１７から、Ｎ、ガス及び０．ガスをそれぞれ純化器
１８．１９を経て熱処理装置本体６Ａ内に送り出した。The frying pan 2 obtained by the above method is heated to the heat treatment apparatus main body 6.
Installed on the shelf in A, N, gas cylinder 16 and 0. From the gas cylinder 17, N, gas and 0. The gases were sent into the heat treatment apparatus main body 6A through purifiers 18 and 19, respectively.
このようにして熱処理装置本体６Ａ内は０１／Ｎｔ＝１
／２０〜１１５の雰囲気に保ち、この条件でフライパン
をヒーター２０によって３５０℃に加熱した。その結果
、表面に濃金色の美しい色調のＴｉＮ被膜を形成したフ
ライパン（実施例１という）が得られた。In this way, the inside of the heat treatment apparatus main body 6A is 01/Nt=1
The frying pan was heated to 350° C. with the heater 20 under these conditions. As a result, a frying pan (referred to as Example 1) having a TiN coating with a beautiful deep golden color formed on the surface was obtained.
同様にしてフライパン２を熱処理装置２３内の棚２７に
設置し、Ｎ、ガスボンベ２４から、Ｎ、ガス純化器２５
を経て熱処理装置本体２３Ａ内に送り出した。このよう
にして熱処理装置本体２３Ａ内をＮ、雰囲気（７６０〜
７６５ Ｔｏｒｒ）に保ち、この条件で、フライパンを
ヒーター２６によって３５０℃に加熱した。その結果、
表面に純金色の美しい色調のＴｉＮ被膜を形成したフラ
イパン（実施例２という）が得られた。In the same way, the frying pan 2 is installed on the shelf 27 in the heat treatment device 23, and the N gas cylinder 24 is heated to the N gas purifier 25.
It was then sent out into the heat treatment apparatus main body 23A. In this way, the inside of the heat treatment apparatus main body 23A is filled with N atmosphere (760~
765 Torr), and under these conditions, the frying pan was heated to 350° C. by the heater 26. the result,
A frying pan (referred to as Example 2) having a TiN coating with a beautiful pure gold color formed on the surface was obtained.
上記操作により得られた実施例１と実施例２のフライパ
ンについて、加熱によるＴｉＮ被膜の色調変化、食品の
耐焼き付き性、耐摩耗性をテストした。The frying pans of Example 1 and Example 2 obtained by the above operations were tested for color change of the TiN coating due to heating, food sticking resistance, and abrasion resistance.
まず加熱による変色について、実施例１のフライパン及
び色調安定化処理を施していないＴｉＮを形成したフラ
イパン（比較例という）を、それぞれ３００°Ｃで加熱
した。その結果、実施例Ｉのフライパンに変色は見られ
なかったが、比較例のフライパンは黒味を帯びた暗黄色
に変色した。また、この加熱テスト後の各々のフライパ
ンについてＸ線回折を行った。その結果を第６図に示す
。First, regarding discoloration due to heating, the frying pan of Example 1 and the frying pan formed of TiN without color stabilization treatment (referred to as a comparative example) were each heated at 300°C. As a result, no discoloration was observed in the frying pan of Example I, but the frying pan of Comparative Example was discolored to a blackish dark yellow. Moreover, X-ray diffraction was performed on each frying pan after this heating test. The results are shown in FIG.
なお第６図中記号Ａは、実施例１のＴｉＮコーティング
を設けたフライパンを３００℃加熱したもの、Ｂは比較
例で無コーテイングのフライパンを３００℃加熱したも
の、Ｃは比較例でＴｉＮコーティングを設けたフライパ
ンを示す。また実施例２のフライパンについても３００
℃加熱テストを行ったが変色は見られなかった。In Figure 6, symbol A is the frying pan provided with the TiN coating of Example 1 heated to 300°C, B is the comparative example that is the uncoated frying pan heated to 300°C, and C is the comparative example with the TiN coating. Shows the frying pan installed. Also, regarding the frying pan of Example 2, 300
A heating test at ℃ was performed, but no discoloration was observed.
また食品の焼き付き性については、実施例１と実施例２
のフライパンを用いて、魚と餅を焼いて永い期間にわた
りテストしたところ、双方ともに焼き付きは全く見られ
なかった。In addition, regarding the sticking property of food, Example 1 and Example 2
When we tested fish and rice cakes over a long period of time using this frying pan, no burning was observed in either of them.
また耐摩耗性については、実施例Ｉと実施例２のフライ
パンの表面を金属たわしを用いて強力に擦過したが、双
方とも膜表面の傷つきや膜の剥離は見られず、優れた耐
摩耗性を有することが確認された。Regarding abrasion resistance, the surfaces of the frying pans of Example I and Example 2 were strongly rubbed using a metal scrubber, but in both cases, no scratches on the membrane surface or peeling of the membrane were observed, indicating excellent abrasion resistance. It was confirmed that the
「発明の効果」
以上述べたように、本発明におけるＴｉＮ被膜の形成方
法によれば、ＴｉＮ被膜中に残存するＴｉを酸素と窒素
の混合雰囲気中あるいは窒素単独雰囲気中で加熱してＴ
ｉＮ被膜の色調を安定化させることができる。"Effects of the Invention" As described above, according to the method for forming a TiN film according to the present invention, Ti remaining in the TiN film is heated in a mixed atmosphere of oxygen and nitrogen or in a nitrogen atmosphere alone.
The color tone of the iN film can be stabilized.
また本発明方法により得られたフライパンは、その表面
に美しい金色の色調をもつＴｉＮ被膜を形成しているの
でフライパンの装飾性が向上し、高級感を付与できる。Furthermore, since the frying pan obtained by the method of the present invention has a TiN coating with a beautiful golden color formed on its surface, the decorativeness of the frying pan is improved and a sense of luxury can be imparted to the frying pan.
またこのフライパンのＴｉＮ被膜は色調安定化のための
熱処理がなされているので、フライパンの美しい金色の
色調が永い期間にわたり加熱時に変化することがない。Additionally, the TiN coating on this frying pan has been heat-treated to stabilize its color, so the beautiful golden color of the frying pan will not change during heating over a long period of time.
第１図は、本発明のＴｉＮ被膜形成方法を実施する装置
の一例を示す概略構成図、第２図は、第１図で示す装置
で用いたイオンブレーティング装置を示す概略構成図、
第３図は、第１図で示す装置で用いた熱処理装置の一例
を示す概略構成図、第４図は、第１図で示す装置で用い
た熱処理装置の他の例を示す概略構成図、第５図は本発
明の実施により得られたフライパンの斜視図、第６図は
本発明の詳細な説明するためのＸ線回折図である。
ｌ・・フライパン基体、２・・・フライパン（ＴｉＮ形
成）３・・・フライパン（色調安定化）、４・・・研磨
洗浄装置、５・・・イオンブレーティング装置、５Ａ・
・・イオンブレーティング装置本体、６・・・熱処理装
置、６Ａ・・・熱処理装置本体、２３・・・熱処理装置
、２３Ａ・・・熱処理装置本体。FIG. 1 is a schematic configuration diagram showing an example of an apparatus for carrying out the TiN film forming method of the present invention, FIG. 2 is a schematic configuration diagram showing an ion blating device used in the apparatus shown in FIG. 1,
3 is a schematic configuration diagram showing an example of the heat treatment apparatus used in the apparatus shown in FIG. 1, FIG. 4 is a schematic configuration diagram showing another example of the heat treatment apparatus used in the apparatus shown in FIG. 1, FIG. 5 is a perspective view of a frying pan obtained by carrying out the present invention, and FIG. 6 is an X-ray diffraction diagram for explaining the present invention in detail. l... Frying pan base, 2... Frying pan (TiN formation), 3... Frying pan (color stabilization), 4... Polishing cleaning device, 5... Ion blating device, 5A...
...Ion blating device main body, 6... Heat treatment device, 6A... Heat treatment device main body, 23... Heat treatment device, 23A... Heat treatment device main body.
Claims (4)
を酸素と窒素の混合雰囲気中で加熱し、窒化チタン被膜
表面に透明でかつ安定な酸化チタン薄膜を形成させる色
調安定化処理を行うことを特徴とする窒化チタン被膜の
形成方法。1. After forming a titanium nitride film on the surface of the substrate, this substrate is heated in a mixed atmosphere of oxygen and nitrogen to perform color stabilization treatment to form a transparent and stable titanium oxide thin film on the surface of the titanium nitride film. Characteristic method of forming titanium nitride film.
と窒素の混合雰囲気中で加熱し、窒化チタン被膜表面に
透明でかつ安定な酸化チタン薄膜を形成させて色調安定
化処理を行って得られたことを特徴とする調理用鍋類。2. A titanium nitride film is formed on the surface of the pot base, and this is heated in a mixed atmosphere of oxygen and nitrogen to form a transparent and stable titanium oxide thin film on the surface of the titanium nitride film to stabilize the color tone. Cooking pots characterized by the fact that
を窒素雰囲気中で加熱し、窒化チタン被膜中に窒素を拡
散させる色調安定化処理を行うことを特徴とする窒化チ
タン被膜の形成方法。3. A method for forming a titanium nitride film, which comprises forming a titanium nitride film on the surface of a substrate, heating the substrate in a nitrogen atmosphere, and performing color stabilization treatment to diffuse nitrogen into the titanium nitride film.
雰囲気中で加熱し、窒化チタン被膜中に窒素を拡散させ
て得られたことを特徴とする調理用鍋類。4. A cooking pot characterized by being obtained by forming a titanium nitride film on the surface of a pot base, heating the film in a nitrogen atmosphere, and diffusing nitrogen into the titanium nitride film.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2176968A JPH0774448B2 (en) | 1990-07-04 | 1990-07-04 | Cooking pots |
| EP90910902A EP0489914B1 (en) | 1990-06-29 | 1990-07-31 | Method of forming titanium nitride coating and pan made by this method |
| AU60531/90A AU648258B2 (en) | 1990-06-29 | 1990-07-31 | Method of forming titanium nitride film and vessel coated by same |
| PCT/JP1990/000974 WO1992000032A1 (en) | 1990-06-29 | 1990-07-31 | Method of forming titanium nitride coating and pan made by this method |
| DE69026619T DE69026619T2 (en) | 1990-06-29 | 1990-07-31 | METHOD FOR FORMING A TITANIUM NITRIDE COVER LAYER AND PAN PRODUCED BY THIS METHOD |
| CA002065303A CA2065303A1 (en) | 1990-06-29 | 1990-07-31 | Method for forming titanium nitride film and vessel coated by same |
| CN90107238.9A CN1057867A (en) | 1990-06-29 | 1990-09-03 | Be used to form the method that titanium nitride coating and manufacturing are coated with this plated film container |
| US08/171,248 US5447803A (en) | 1990-06-29 | 1993-12-20 | Method for forming titanium nitride film and vessel coated by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2176968A JPH0774448B2 (en) | 1990-07-04 | 1990-07-04 | Cooking pots |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32883994A Division JPH07207446A (en) | 1994-12-28 | 1994-12-28 | Forming method of titanium coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0466667A true JPH0466667A (en) | 1992-03-03 |
| JPH0774448B2 JPH0774448B2 (en) | 1995-08-09 |
Family
ID=16022861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2176968A Expired - Lifetime JPH0774448B2 (en) | 1990-06-29 | 1990-07-04 | Cooking pots |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774448B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995027426A1 (en) * | 1994-04-06 | 1995-10-19 | Kato Manufacturing Corporation Limited | Utensils for eating, drinking and cooking |
| US7093340B2 (en) * | 1997-12-16 | 2006-08-22 | All-Clad Metalcrafters Llc | Stick resistant ceramic coating for cookware |
| WO2024235924A1 (en) * | 2023-05-12 | 2024-11-21 | Matthias Gurris | Cookware having a decorative layer and method for producing a decorative layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5836671A (en) * | 1981-08-14 | 1983-03-03 | ザ・パ−キン−エルマ−・コ−ポレイション | Plasma flame spray gun and cooling of nozzle thereof |
| JPS6320460A (en) * | 1986-07-14 | 1988-01-28 | Nippon Kokan Kk <Nkk> | Heat treatment method for ion plating treated materials |
-
1990
- 1990-07-04 JP JP2176968A patent/JPH0774448B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5836671A (en) * | 1981-08-14 | 1983-03-03 | ザ・パ−キン−エルマ−・コ−ポレイション | Plasma flame spray gun and cooling of nozzle thereof |
| JPS6320460A (en) * | 1986-07-14 | 1988-01-28 | Nippon Kokan Kk <Nkk> | Heat treatment method for ion plating treated materials |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995027426A1 (en) * | 1994-04-06 | 1995-10-19 | Kato Manufacturing Corporation Limited | Utensils for eating, drinking and cooking |
| US7093340B2 (en) * | 1997-12-16 | 2006-08-22 | All-Clad Metalcrafters Llc | Stick resistant ceramic coating for cookware |
| WO2024235924A1 (en) * | 2023-05-12 | 2024-11-21 | Matthias Gurris | Cookware having a decorative layer and method for producing a decorative layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774448B2 (en) | 1995-08-09 |
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