JPH042539B2 - - Google Patents
Info
- Publication number
- JPH042539B2 JPH042539B2 JP60149226A JP14922685A JPH042539B2 JP H042539 B2 JPH042539 B2 JP H042539B2 JP 60149226 A JP60149226 A JP 60149226A JP 14922685 A JP14922685 A JP 14922685A JP H042539 B2 JPH042539 B2 JP H042539B2
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- titanium
- layer
- powder
- titanium nitride
- 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.)
- Expired - Lifetime
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 9
- 230000007423 decrease Effects 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 34
- 239000000843 powder Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 21
- 239000004408 titanium dioxide Substances 0.000 description 15
- 238000005245 sintering Methods 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- -1 hafnium nitride Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Products (AREA)
Description
＜産業上の利用分野＞
本発明は表面層が窒化チタンで内部が酸窒化チ
タンよりなる焼結体に関する。
＜従来技術およびその問題点＞
IVa族、Va族金属の窒化物、即ち、窒化チタ
ン、窒化ジルコニウム、窒化ハフニウム、窒化ニ
オブ等は耐熱性、耐食性に優れた高硬度化合物
で、美麗な黄金光沢を有する。さらに、これらの
化合物は導電性を有するため、ほこり等が付着し
にくい。それゆえ、フイルムや磁気テープの巻き
取りのガイド部材や、合成繊維やフイルム等を製
造する際のガイド部材として極めて優れた特性を
有し、また装飾用としても有用である。
これらの化合物のなかでも、窒化チタンは低比
重であり、比較的安価であるため最も一般的に使
用されている。
窒化チタンの焼結体は、従来、二酸化チタンと
炭素材料を混合した粉末を窒素雰囲気中で還元窒
化することによつて、窒化チタン粉末を得、該粉
末を圧縮成形し、真空中またはアルゴン等の不活
性雰囲気中において1700℃以上の高温で焼結して
製造している。しかし、前記方法で得られる窒化
チタン粉末は粒度が粗く、焼結に長時間を要し、
しかも緻密な焼結体を得ることができない。緻密
な焼結体を得ようとして、より高温で焼結を行な
うと、脱窒を起す。
それゆえ、他の化合物の焼結体の表面に窒化チ
タンをコーテイングすることも行なわれている
が、母材と窒化チタンの被膜が剥離し易いという
欠点があり、さらに被膜自体の強度にも問題があ
る。
＜発明の構成＞
本発明は上記従来の問題点を解決するものであ
つて、本発明によれば、表面層が主に窒化チタン
であり、該表面層から内部にかけて窒素含有量が
次第に減少する一方酸素含有量が増加し、内部が
酸窒化チタンである焼結体が提供される。
本発明の焼結体は表面層が窒化チタンであり、
内部が酸窒化チタンであつて、表面の窒化チタン
層と内部の酸窒化チタン層との間には、表面から
内部に進むにつれて窒素含有量が減少する一方酸
素含有量が増加する中間層が存在する。即ち本発
明の焼結体は表面の窒化チタン層と内部の酸窒化
チタン層間に上記中間層が介在する漸次的な二重
構造を有する。表面層および内部層の窒素含有量
および酸素含有量はそれぞれ次の表の通りであ
る。
<Industrial Application Field> The present invention relates to a sintered body whose surface layer is made of titanium nitride and whose interior is made of titanium oxynitride. <Prior art and its problems> Nitrides of group IVa and Va group metals, such as titanium nitride, zirconium nitride, hafnium nitride, and niobium nitride, are high-hardness compounds with excellent heat resistance and corrosion resistance, and have a beautiful golden luster. have Furthermore, since these compounds have conductivity, dust and the like are less likely to adhere to them. Therefore, it has extremely excellent properties as a guide member for winding up films and magnetic tapes, and in the production of synthetic fibers, films, etc., and is also useful for decorative purposes. Among these compounds, titanium nitride is the most commonly used because it has a low specific gravity and is relatively inexpensive. Sintered bodies of titanium nitride have conventionally been obtained by reducing and nitriding a powder mixture of titanium dioxide and a carbon material in a nitrogen atmosphere, compression molding the powder, and molding the powder in a vacuum or with argon, etc. It is manufactured by sintering at a high temperature of 1700℃ or higher in an inert atmosphere. However, the titanium nitride powder obtained by the above method has a coarse grain size and requires a long time to sinter.
Moreover, a dense sintered body cannot be obtained. If sintering is performed at a higher temperature in an attempt to obtain a dense sintered body, denitrification will occur. Therefore, coating titanium nitride on the surface of sintered bodies of other compounds has been carried out, but this has the disadvantage that the titanium nitride coating easily peels off from the base material, and there are also problems with the strength of the coating itself. There is. <Structure of the Invention> The present invention solves the above conventional problems, and according to the present invention, the surface layer is mainly made of titanium nitride, and the nitrogen content gradually decreases from the surface layer to the inside. On the other hand, a sintered body with an increased oxygen content and a titanium oxynitride interior is provided. The sintered body of the present invention has a surface layer of titanium nitride,
The interior is titanium oxynitride, and between the titanium nitride layer on the surface and the titanium oxynitride layer inside, there is an intermediate layer in which the nitrogen content decreases while the oxygen content increases from the surface to the interior. do. That is, the sintered body of the present invention has a gradual double structure in which the intermediate layer is interposed between the titanium nitride layer on the surface and the titanium oxynitride layer inside. The nitrogen content and oxygen content of the surface layer and internal layer are shown in the following table, respectively.
【表】
本発明の焼結体はこのように表面から内部にか
けて窒素含有量と酸素含有量とが徐々に変化する
組成であるため、従来のように表面に窒化チタン
をコーテイングしたものに比べて表面の窒化チタ
ン層と内部の酸窒化チタン層との結合が極めて強
固である。更に焼結体の密度も格段に大きい。因
に窒化チタン粉末を圧縮成形して焼結した従来の
焼結体はピツカーズ硬度が800〜1500Kg／mm2程度、
密度が90〜97％程度であるのに対し本発明の焼結
体はピツカース硬度および密度がそれぞれ1700〜
1850Kg／mm2、98％以上であり従来の焼結体に比べ
て緻密、かつ強固である。また従来の焼結体の導
電性は１×10-3Ωcm程度であるのに比べ本発明の
焼結体は１〜５×10-4Ωcmであり導電性もすぐれ
ている。
次に上記焼結体は、酸窒化チタン粉末を圧縮成
形し、1200〜1700℃の温度範囲において窒素ある
いはアンモニア雰囲気中で焼結することによつて
得られる。原料の酸窒化チタン粉末は二酸化チタ
ン粉末を700〜1000℃の温度範囲においてアンモ
ニアガスと反応させて得られるものが好適であ
る。アンモニア雰囲気中で二酸化チタン粉末を
700〜1000℃の温度範囲で加熱すると、二酸化チ
タンの還元と窒化が起つて酸窒化チタン粉末が得
られる。この温度範囲では焼結は殆ど起らないの
で、微細な二酸化チタン粉末を原料として使用す
ると、そのままの微細な酸窒化チタンを得ること
ができる。
酸窒化チタンの原料となる二酸化チタンは、ど
のような製法のものでもよいが、微細な酸窒化チ
タン粉末を得るためには、できるだけ微細な二酸
化チタン粉末を用いなければならない。二酸化チ
タン粉末とアンモニアの反応は700〜1000℃の温
度範囲において１時間以上行なう。700℃未満で
は反応速度が充分でなく、未反応の二酸化チタン
が多量に残留し、高強度の焼結体を得るための原
料としては不適である。また1000℃を超える温度
では粒子の結合が起り、得られる酸窒化チタン粉
末は粗大なものとなるので焼結原料としては同様
に不適である。
上記のようにして得られた酸窒化チタン粉末を
所望の形状に圧縮成形する。この時、バインダー
としてPVA、CMC、PVP等の粘結物質（糊料）
を少量添加しておく方が圧粉体の強度を高め取扱
を容易にする。プレス圧は特に限定されない。
この圧粉体をアンモニア雰囲気または窒素雰囲
気で1200〜1700℃の温度範囲で焼結する。
焼結温度を1200〜1700℃に限定する理由は、
1200℃未満では、いかに長時間焼結しても密度は
上がらず、充分な硬度を有する焼結体が得られな
い。また1700℃を超える温度で焼結しても、焼結
時間は短縮されないのみならず、脱窒素が起りは
じめ、緻密な焼結体を得ることができない。また
焼結温度に達するまでの昇温速度は500℃／hr以
下が望ましい。500℃／hrを超える速度で昇温す
ると、ひび割れを生じたり、表面の窒化チタン層
が剥離することがある。
なお、内部の酸窒化チタンの酸素量は二酸化チ
タン粉末をアンモニアと反応させる際の温度と反
応時間を調整することによつて制御できる。
更に、圧粉体をアンモニアあるいは窒素雰囲気
中で焼成する際、アンモニアあるいは窒素50vol
％未満の不活性ガスないし水素ガスを混合して表
面の窒化チタン層の厚さを制御することが出来
る。尚、酸窒化チタンの粉末を得る際、二酸化チ
タンとアンモニアとの反応が充分でないと、焼結
体の表面に二酸化チタンが残存する場合がある
が、表面層の酸素量が40％以下の場合の硬度に悪
影響を与えないので差し支えない。またこの場合
内部層にも二酸化チタンが少量残存するが殆ど影
響ない。
以上の製造方法により表面が窒化チタンで内部
が酸窒化チタンのままである焼結体が得られる。
この焼結体は微細な酸窒化チタン粉末を焼結原料
とするために短時間で緻密な焼結体を得ることが
出来る。
＜実施例および比較例＞
実施例 １
平均粒径0.03μの二酸化チタンを800℃の温度で
アンモニア雰囲気中において４時間反応させて得
られた粉末にPVA1％を加え造粒した粉末を1t／
cm2の圧力で30×30mmの金型を用いて８mmの厚さの
圧粉体とした。この圧粉体をアンモニア雰囲気中
で1600℃において２時間焼結したところ黄金色の
焼結体が得られた。
この焼結体の表面から0.1mmのところまでは1.7
％のTiO2が混在する窒化チタン層からなり、0.3
mmより中心部は、酸素量8.2％、窒素量16.7％チ
タン量75.1％の組成より成る層によつて形成され
ていた。また表面から0.1mm〜0.3mmの層は徐々に
酸素含有量が増加し、窒素量が減少している酸窒
化チタン層であつた。この焼結体のピツカース硬
度は1830Kg／mm2であつた。
実施例 ２
実施例１と同じ圧粉体を窒素雰囲気中で1300℃
で３時間焼結し、得られた焼結体は表面から0.05
mmのところまでは4.0％のTiO2が混在する窒化チ
タン層よりなり、0.05〜0.2mmの層は徐々に酸素
含有量が増加、窒素含有量が減少し、0.2mmより
中心部は酸素量8.0％、窒素量17.0％の酸窒化チ
タン層より成つていた。この焼結体のビツカース
硬度は1790Kg／mm2であつた。色調は実施例１で得
られたものとほぼ同じであつた。
実施例 ３
実施例１、２と同じ二酸化チタン粉末を900℃
の温度で３時間反応させた粉体を実施例１、２と
同じ条件で圧粉体とした。この圧粉体を窒素を
20vol％のアルゴンで希釈した雰囲気下で1500℃
において３時間焼結した。この焼結体は表面から
0.07mmのところまでは2.3％のTiO2が混在する窒
化チタン層より成り、0.07〜0.25mmの層は徐々に
酸素含有量が増加、窒素含有量が減少し、0.25mm
より中心部は酸素量8.0％窒素量17.1％の酸窒化
チタン層で形成されていた。この焼結体の色調は
実施例１、２とほぼ同じ黄金色で、ピツカース硬
度は1810Kg／mm2であつた。
比較例
平均粉末1.0μの窒化チタン粉末を実施例と同じ
条件で圧粉体とし窒素雰囲気中で1700℃で４時間
焼結した。得られた焼結体の色調は暗い赤色でピ
ツカース硬度は900Kg／mm2であつた。[Table] Since the sintered body of the present invention has a composition in which the nitrogen content and oxygen content gradually change from the surface to the inside, it is more The bond between the titanium nitride layer on the surface and the titanium oxynitride layer inside is extremely strong. Furthermore, the density of the sintered body is also significantly higher. Incidentally, the conventional sintered body made by compression molding and sintering titanium nitride powder has a Pickers hardness of about 800 to 1500 Kg/ mm2 ,
While the density is about 90-97%, the sintered body of the present invention has a Pickkers hardness and a density of 1700-97%.
1850Kg/mm 2 , more than 98%, denser and stronger than conventional sintered bodies. Further, while the conventional sintered body has a conductivity of about 1×10 −3 Ωcm, the sintered body of the present invention has an excellent conductivity of 1 to 5×10 −4 Ωcm. Next, the above-mentioned sintered body is obtained by compression molding titanium oxynitride powder and sintering it in a nitrogen or ammonia atmosphere at a temperature range of 1200 to 1700°C. The raw material titanium oxynitride powder is preferably one obtained by reacting titanium dioxide powder with ammonia gas at a temperature range of 700 to 1000°C. Titanium dioxide powder in an ammonia atmosphere
When heated in a temperature range of 700 to 1000°C, titanium dioxide is reduced and nitrided to obtain titanium oxynitride powder. Sintering hardly occurs in this temperature range, so if fine titanium dioxide powder is used as a raw material, fine titanium oxynitride can be obtained as is. Titanium dioxide, which is a raw material for titanium oxynitride, may be manufactured by any method, but in order to obtain fine titanium oxynitride powder, it is necessary to use titanium dioxide powder as fine as possible. The reaction between titanium dioxide powder and ammonia is carried out at a temperature range of 700 to 1000°C for over 1 hour. If the temperature is less than 700°C, the reaction rate is insufficient and a large amount of unreacted titanium dioxide remains, making it unsuitable as a raw material for obtaining a high-strength sintered body. In addition, at temperatures exceeding 1000°C, particle bonding occurs and the resulting titanium oxynitride powder becomes coarse, making it similarly unsuitable as a sintering raw material. The titanium oxynitride powder obtained as described above is compression molded into a desired shape. At this time, binders such as PVA, CMC, PVP, etc.
It is better to add a small amount of to increase the strength of the green compact and make it easier to handle. Press pressure is not particularly limited. This green compact is sintered in an ammonia atmosphere or a nitrogen atmosphere at a temperature in the range of 1200 to 1700°C. The reason for limiting the sintering temperature to 1200-1700℃ is
If the temperature is less than 1200°C, no matter how long the sintering time is, the density will not increase and a sintered body with sufficient hardness will not be obtained. Furthermore, even if sintering is performed at a temperature exceeding 1700°C, not only will the sintering time not be shortened, but denitrification will begin to occur, making it impossible to obtain a dense sintered body. Further, the temperature increase rate until reaching the sintering temperature is desirably 500°C/hr or less. If the temperature is increased at a rate exceeding 500°C/hr, cracks may occur or the titanium nitride layer on the surface may peel off. The amount of oxygen in the titanium oxynitride inside can be controlled by adjusting the temperature and reaction time when titanium dioxide powder is reacted with ammonia. Furthermore, when firing the green compact in an ammonia or nitrogen atmosphere, 50vol of ammonia or nitrogen is added.
The thickness of the titanium nitride layer on the surface can be controlled by mixing less than % of inert gas or hydrogen gas. When obtaining titanium oxynitride powder, if the reaction between titanium dioxide and ammonia is not sufficient, titanium dioxide may remain on the surface of the sintered body, but if the amount of oxygen in the surface layer is 40% or less. There is no problem as it does not adversely affect the hardness of the material. In this case, a small amount of titanium dioxide also remains in the inner layer, but it has almost no effect. By the above manufacturing method, a sintered body having a titanium nitride surface and a titanium oxynitride interior can be obtained.
Since this sintered body uses fine titanium oxynitride powder as a sintering raw material, a dense sintered body can be obtained in a short time. <Examples and Comparative Examples> Example 1 1% PVA was added to the powder obtained by reacting titanium dioxide with an average particle size of 0.03μ in an ammonia atmosphere at a temperature of 800°C for 4 hours.
A green compact with a thickness of 8 mm was made using a mold of 30 x 30 mm at a pressure of cm 2 . When this green compact was sintered at 1600° C. for 2 hours in an ammonia atmosphere, a golden yellow sintered body was obtained. The distance from the surface of this sintered body to 0.1mm is 1.7
Consisting of a titanium nitride layer mixed with 0.3% TiO2
The center part from mm was formed by a layer having a composition of 8.2% oxygen, 16.7% nitrogen, and 75.1% titanium. The layer 0.1 mm to 0.3 mm from the surface was a titanium oxynitride layer in which the oxygen content gradually increased and the nitrogen content decreased. The Pickers hardness of this sintered body was 1830 Kg/mm 2 . Example 2 The same green compact as in Example 1 was heated at 1300°C in a nitrogen atmosphere.
The sintered body was sintered for 3 hours at a temperature of 0.05 mm from the surface.
The layer up to 0.05 mm consists of a titanium nitride layer containing 4.0% TiO 2 , and the layer from 0.05 to 0.2 mm gradually increases in oxygen content and decreases in nitrogen content, and from 0.2 mm onwards, the oxygen content is 8.0% in the center. %, and a titanium oxynitride layer with a nitrogen content of 17.0%. The Bitkers hardness of this sintered body was 1790 Kg/mm 2 . The color tone was almost the same as that obtained in Example 1. Example 3 The same titanium dioxide powder as in Examples 1 and 2 was heated to 900°C.
The powder that was reacted at a temperature of 3 hours for 3 hours was made into a green compact under the same conditions as in Examples 1 and 2. This green compact is heated with nitrogen.
1500℃ under an atmosphere diluted with 20vol% argon
It was sintered for 3 hours. This sintered body is
Up to 0.07mm, it consists of a titanium nitride layer mixed with 2.3% TiO2 , and in the layer from 0.07 to 0.25mm, the oxygen content gradually increases and the nitrogen content decreases until 0.25mm.
The central part was formed of a titanium oxynitride layer with an oxygen content of 8.0% and a nitrogen content of 17.1%. The color tone of this sintered body was almost the same golden yellow as in Examples 1 and 2, and the Pickkers hardness was 1810 Kg/mm 2 . Comparative Example Titanium nitride powder with an average powder size of 1.0 μm was made into a compact under the same conditions as in the example and sintered at 1700° C. for 4 hours in a nitrogen atmosphere. The color of the obtained sintered body was dark red, and the Pickkers hardness was 900 Kg/mm 2 .
Claims (1)
ら内部にかけて窒素含有量が次第に減少する一方
酸素含有量が増加し、内部が酸窒化チタンである
表面が窒化チタンで内部が酸窒化チタンからなる
焼結体。 ２ 表面層の窒素含有量が21重量％以上であり、
内部の酸素含有量が２〜25重量％、窒素含有量10
〜21重量％である特許請求の範囲第１項の焼結
体。[Claims] 1. The surface layer is mainly made of titanium nitride, and the nitrogen content gradually decreases from the surface layer to the inside, while the oxygen content increases, and the inside is made of titanium oxynitride and the surface is made of titanium nitride. A sintered body whose interior is made of titanium oxynitride. 2 The nitrogen content of the surface layer is 21% by weight or more,
Internal oxygen content is 2-25% by weight, nitrogen content is 10%
21% by weight of the sintered body of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60149226A JPS6212669A (en) | 1985-07-09 | 1985-07-09 | Sintered body whose surface is titanium oxide and inside is titanium oxynitirde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60149226A JPS6212669A (en) | 1985-07-09 | 1985-07-09 | Sintered body whose surface is titanium oxide and inside is titanium oxynitirde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6212669A JPS6212669A (en) | 1987-01-21 |
| JPH042539B2 true JPH042539B2 (en) | 1992-01-20 |
Family
ID=15470619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60149226A Granted JPS6212669A (en) | 1985-07-09 | 1985-07-09 | Sintered body whose surface is titanium oxide and inside is titanium oxynitirde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6212669A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5415194B2 (en) * | 2009-09-14 | 2014-02-12 | 東芝ホクト電子株式会社 | Thermal print head and manufacturing method thereof |
-
1985
- 1985-07-09 JP JP60149226A patent/JPS6212669A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6212669A (en) | 1987-01-21 |
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