JPH0225559A - Nitriding treatment for ti or ti alloy - Google Patents
Nitriding treatment for ti or ti alloyInfo
- Publication number
- JPH0225559A JPH0225559A JP63174600A JP17460088A JPH0225559A JP H0225559 A JPH0225559 A JP H0225559A JP 63174600 A JP63174600 A JP 63174600A JP 17460088 A JP17460088 A JP 17460088A JP H0225559 A JPH0225559 A JP H0225559A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- gas
- nitriding
- atmosphere
- nitriding treatment
- 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
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 45
- 238000005121 nitriding Methods 0.000 title claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 34
- 239000010936 titanium Substances 0.000 description 38
- 239000000956 alloy Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 238000005468 ion implantation Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910001007 Tl alloy Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910001295 No alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ＴｉまたＴｉ合金からなる材料の表面の窒化
処理法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for nitriding the surface of a material made of Ti or a Ti alloy.
（従来の技術〉
ＴＩまたはＴ１合金は、耐食性材料として床机に用いら
れており、従来より海水熱交換器用チューブとして用い
られる他、その軽量性から、航空機用材料としても用い
られている。(Prior Art) TI or T1 alloy has been used as a corrosion-resistant material for floor desks, and has been conventionally used as tubes for seawater heat exchangers, as well as as a material for aircraft due to its light weight.
ところで、近年になってＴＩまたはＴｉ合金はその耐食
性、特に優れた耐海水性のために海洋構造物用６材料と
しての用途が検討されはじめている。ところが、Ｔ１ま
たはＴｉ合金はその靭性が比較的劣っているため海洋構
遺物材料としてこのまま用いると、最も重要な特性であ
る疲労強度が不足してしまうことになる。かかる疲労強
度の不足は、構造物用材料として重大な危険を招来する
恐れがあるものであって、設計変更を含めた早急な対策
が強く望まれている。つまりＴｉまたはＴｉ合金の疲労
強度を向上させることにより、海洋構造物用材料として
ＴｉまたはＴｉ合金を用いることが望まれているのであ
る。Incidentally, in recent years, TI or Ti alloys have begun to be considered for use as materials for marine structures because of their corrosion resistance, particularly their excellent seawater resistance. However, T1 or Ti alloys have relatively poor toughness, so if they are used as is as a material for marine structures, they will lack fatigue strength, which is the most important property. Such lack of fatigue strength may pose a serious danger to structural materials, and immediate countermeasures, including design changes, are strongly desired. In other words, it is desired to use Ti or Ti alloys as materials for marine structures by improving the fatigue strength of Ti or Ti alloys.
−ｍ的に金属材料の疲労強度を向上させるには、転位が
すべり線に沿って金属表面に抜けることを抑制するため
金属表面の硬度を上げることが有効であると言われてい
る。In order to improve the fatigue strength of metal materials in terms of -m, it is said to be effective to increase the hardness of the metal surface in order to suppress dislocations from passing through the metal surface along slip lines.
そこでＴｉまたはＴ１合金においてもその表面の硬度を
、Ｅげることが有効であると考えられ、従来よりＴｉま
たはＴｉ合金の表面を硬化する方法が種々提案されてお
り、例えば以下に示すような方法がある。Therefore, it is thought that it is effective to reduce the surface hardness of Ti or T1 alloy, and various methods have been proposed to harden the surface of Ti or Ti alloy. There is a way.
（ｉ）イオン注入法
イオン注入法は、真空中でイオンを加速し、金属材料の
表面に打ち込む方法である。この方法において用いるイ
オン注入装置の概略図を第３図に示す。イオン発生部で
注入すべきイオンは、イオン化され、数１０ＫＶ程度の
電圧で引き出されて、質量分析部に導かれる。質量分析
部ではイオン発生部で作られたイオンのうち、一定の（
質量／電青）比をもったイオンだけが選ばれ、加速部で
イオンは高エネルギーに加速され、エンドステーション
で試料の原子と衝突しながら表面層を形成する方法であ
る。(i) Ion implantation method The ion implantation method is a method in which ions are accelerated in a vacuum and implanted into the surface of a metal material. A schematic diagram of the ion implantation apparatus used in this method is shown in FIG. The ions to be injected in the ion generator are ionized, extracted with a voltage of approximately several tens of kilovolts, and guided to the mass spectrometer. In the mass spectrometer, a certain number of ions (
In this method, only ions with a high mass/electronic energy ratio are selected, and the ions are accelerated to high energy in the acceleration section, and then collide with the atoms of the sample at the end station, forming a surface layer.
（ｉｉ ）イオン窒化法
イオン窒化法は、第４図にこの方法において用いるイオ
ン窒化装置の概略図を示したように通常直流グロー放電
を用いて、真空中でグロー放電によるプラズマを発生さ
せ、プラズマ内のガス（ここではＮ、）をイオン化した
上で、陰極降下現象により該イオンを加速して金属材料
の表面に衝突させて窒化を行う方法である（Ｐｉ誌「熱
処理」２７巻６号Ｐ３３５〜Ｐ３４１） 。(ii) Ion nitriding method The ion nitriding method normally uses direct current glow discharge to generate plasma by glow discharge in a vacuum, as shown in Figure 4, which is a schematic diagram of the ion nitriding apparatus used in this method. This is a method of nitriding by ionizing the gas (in this case, N) inside the metal material, accelerating the ions using a cathode fall phenomenon, and causing them to collide with the surface of the metal material (Pi magazine, "Heat Treatment" Vol. 27, No. 6, p. 335). ~P341).
（ｉｉｉ ）窒素ガスによる窒化性
上に述べたイオン注入法、イオン窒化法による方法に代
わり最近では、窒素ガスによるＴＩ製品の窒化も実用化
されている（特開昭６２〜１９６３６５号、同６３−４
０５２号等）、この方法は、スポンジチタンに接触させ
た窒素ガスをＴｉ製部材に接触させて窒化を行う方法で
ある。(iii) Nitriding properties using nitrogen gas Instead of the above-mentioned ion implantation method and ion nitriding method, nitriding of TI products using nitrogen gas has recently been put into practical use (JP-A-62-196365, JP-A-1963-63). -4
052, etc.), this method is a method in which nitrogen gas brought into contact with a titanium sponge is brought into contact with a Ti member to perform nitriding.
（発明が解決しようとする謀Ｈ）
しかしながら、これらの方法を用いて海洋構造物用とい
った大型の丁１またはＴｉ合金からなる材料の表面の窒
化処理を行うには、これらの方法に共通ずる次のような
問題があった。すなわちいずれの方法にしても
（＋） 処理用チャンバーを用いて該チャンバー内での
バンチ処理により窒化を行う方法であるので、Ｔｔまた
はＴｉ合金からなる大型の被処理材を収容することがで
きるチャンバーが必要となり、多大な設備費を要するこ
と
（ｉｉ ）処理用チャンバー内を真空にする必要があり
、処理時間が極めて長大となってしまうため処理費用が
大幅に上昇すること
といった問題があり％ＴＩまたはＴｉ合金からなる大型
材料の表面を窒化処理するに際してどの方法も容易には
採用することができなかったのである。(Plot H to be solved by the invention) However, in order to perform nitriding treatment on the surface of a large-sized material made of Ti alloy or Ti alloy for marine structures using these methods, there are certain steps common to these methods. There was a problem like this. In other words, either method is a method in which nitriding is performed by bunching using a (+) processing chamber, so a chamber capable of accommodating a large-sized material to be processed made of Tt or Ti alloy is required. %TI Furthermore, it has not been possible to easily employ any method when nitriding the surface of a large material made of a Ti alloy.
ここに、本発明の目的は、ＴｉまたはＴｉ合金からなる
大型の金属材料の表面を容易にかつ確実に窒化処理する
方法を提供することにある。An object of the present invention is to provide a method for easily and reliably nitriding the surface of a large-sized metal material made of Ti or a Ti alloy.
（課題を解決するための手段）
本発明者は、上記課題を解決するためＴｉまたはＴｉ合
金の表面の窒化処理について種々検討した結果、Ｎｈガ
ス雰囲気でＴＩまたはＴｉ合金を特定した温度範囲で特
定した時間の間、加熱保持をすることによりＴｉまたは
Ｔｉ合金の表面を容易にかつ確実に窒化処理することが
できるとともにＴｉまたはＴｉ合金の熱処理をも兼ねる
ことができることを知り、本発明を完成した。(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted various studies on nitriding the surface of Ti or Ti alloys, and as a result, they have determined that Ti or Ti alloys can be processed in a specified temperature range in an Nh gas atmosphere. The present invention was completed based on the knowledge that the surface of Ti or Ti alloy can be easily and reliably nitrided by heating and holding for a certain period of time, and can also serve as a heat treatment for Ti or Ti alloy. .
ここに本発明の要旨とするところは、ＴｉまたはＴｉ合
金の表面を窒化処理するのに際して、ＮＨｓガス：２０
体積％以上１００体積％未満残部 不活性ガス
である雰囲気中かまたは
Ｎ）Ｉｆｆガス＝１００体積％
である雰囲気中で、４００℃以上８５０℃以下の温度範
囲で１時間以上加熱・保持することを特徴とする、Ｔｉ
またばＴｉ合金の窒化処理法である。The gist of the present invention is that when nitriding the surface of Ti or Ti alloy, NHs gas: 20
Heating and holding in a temperature range of 400°C or more and 850°C or less for 1 hour or more in an atmosphere with an inert gas or an atmosphere where N) If gas = 100% by volume or more with the remainder less than 100% by volume. Features: Ti
Another example is a nitriding method for Ti alloys.
本発明においては、特別なチャンバーは必要とせず、雰
囲気制御が可能な例えば熱処理炉を用いればよく、この
熱処理炉はローラー、ウオーキングビーム等による連続
炉であっても、あるいはバッチ炉であっても良い。In the present invention, there is no need for a special chamber; for example, a heat treatment furnace that can control the atmosphere may be used, and this heat treatment furnace may be a continuous furnace using rollers, a walking beam, etc., or a batch furnace. good.
また本発明は、ＴｉまたはＴ１合金であればその形状、
大きさ等には関係なく適用できるものであり、例えば成
形加工された部材、板状材、管状材またはその他の異形
部材といったあらゆる形状の製品に、またあらゆる大き
さの製品に通用することが可能である。In addition, the present invention also covers the shape of Ti or T1 alloy,
It is applicable regardless of size, and can be applied to products of any shape, such as molded parts, plate materials, tubular materials, or other irregularly shaped parts, and products of any size. It is.
ここにＴｉとは合金成分を含まない純Ｔｉを意味し、ま
たＴｉ合金とはＴｉを主成分とする合金材料を意味する
。Here, Ti means pure Ti containing no alloy components, and Ti alloy means an alloy material containing Ti as a main component.
また本発明は材料の疲労強度の向上を目的とする窒化処
理だけでなく、単に材料の表面硬化を目的とする材料（
耐摩耗性材料）の処理にも広く適用できることは言うま
でもない。In addition, the present invention applies not only nitriding treatment for the purpose of improving the fatigue strength of materials, but also nitriding treatment for the purpose of simply surface hardening of materials (
Needless to say, it can also be widely applied to the treatment of wear-resistant materials.
（作用）
次に本発明をその作用とともに詳述する。なお以下本明
細書において「％」は特にことわりがない限り「体積％
」を意味するものとする。(Function) Next, the present invention will be explained in detail together with its function. In addition, hereinafter in this specification, "%" means "volume %" unless otherwise specified.
” shall mean.
まず窒化処理時に雰囲気条件を８８３： ２０％以上１
００体積％未満および残部不活性ガスかまたはＮＨｓガ
ス：１００％と限定した理由について述べる。First, during the nitriding process, the atmospheric conditions are set to 883: 20% or more1
The reason why it was limited to less than 00% by volume and the remainder being inert gas or NHs gas: 100% will be explained.
雰囲気中のＮＨｉガス量を２０％以上と限定した理由は
窒化処理して得られるＴｉＮの皮膜の硬度を確保するた
めである０本発明者の知見によれば、まずＮＨ，ガスは
高温下においてＮＨｓ ；： Ｎ＋３Ｈという反応によ
り、窒素原子と水素原子に解離する。解離した窒素原子
は直ちにＴｉまたはＴｉ合金内に拡散し、ＴｉまたはＴ
ｉ合金表面部において、ＴｉＮの皮膜を形成するのであ
るが、雰囲気中のＮＨ，ガス量が２０％未満となれば、
Ｔｌ又はＴｉ合金の表面で拡散するＴｉ原子の数が少な
すぎて、表面硬化層の厚さが不足し、表面の硬度が不足
してしまう。The reason why the amount of NHi gas in the atmosphere was limited to 20% or more is to ensure the hardness of the TiN film obtained by nitriding.According to the findings of the present inventors, first, NH gas is NHs;: Dissociates into nitrogen and hydrogen atoms through the reaction N+3H. The dissociated nitrogen atoms immediately diffuse into the Ti or Ti alloy, and the Ti or T
A TiN film is formed on the i-alloy surface, but if the amount of NH and gas in the atmosphere is less than 20%,
If the number of Ti atoms diffusing on the surface of Tl or Ti alloy is too small, the thickness of the hardened surface layer will be insufficient and the hardness of the surface will be insufficient.
ＮＨ！ガス量が２０％以上であれば、どのような範囲で
もＮｉｂガス量に関係なく、材料毎に一定な高硬度の表
面皮膜が得られるのであり、ＮＨ３ガス量が増加すれば
、ＴｉまたはＴｉ合金の表面で拡散するＴｉ原子の数が
増加するため、表面硬化層の厚さが増加することとなる
（Ｎ）＋２ガス量が１００％のとき最も厚い皮膜が得ら
れる）、つまり目的とする表面硬化層の厚さによって、
ＮＨ，ガス量を決定すればよいのである。NH! If the gas amount is 20% or more, a uniform high hardness surface film can be obtained for each material regardless of the Nib gas amount in any range, and if the NH3 gas amount increases, Ti or Ti alloy The thickness of the surface hardening layer increases because the number of Ti atoms diffusing on the surface of Depending on the thickness of the hardened layer,
All that is needed is to determine the amount of NH and gas.
また窒化処理時の雰囲気のＮ）！＊ガス量が１００％で
ないときの残部は、化学反応による、ＴｉＮ以外の表面
層の形成を防止するため、不活性ガスすなわち反応性の
ないガスであればよく特にその種類を限定する必要はな
いが、Ｎｔガス、Ａｒガス等が例示される。Also, the atmosphere during nitriding treatment (N)! *When the gas amount is not 100%, the remaining gas may be an inert gas, that is, a non-reactive gas, and there is no need to limit its type in order to prevent the formation of surface layers other than TiN due to chemical reactions. However, examples include Nt gas and Ar gas.
次に窒化処理時の保持温度を４００〜８５０℃と限定し
た理由について述べる。Next, the reason why the holding temperature during nitriding treatment was limited to 400 to 850°C will be described.
解離したＮ原子はＴｉまたはＴ１合金内に拡散して吹く
が、この時の拡散速度は雰囲気温度と共に大きくなるの
で、雰囲気温度が高くなればなるほど、Ｎ原子がＴＬま
たはＴｉ合金の表面に拡散する深さは増大し、表面のＴ
ｉＨの皮膜の厚さが増大する。このとき、４００℃未満
であると、ＴｉまたはＴｉ合金内へのＮ原子の拡散速度
は極めて小さいためＴｉＮの皮膜の生成は極めて少なく
なるので、実用上窒化処理が行えないこととなるからで
ある。また８５０℃を上限としたのは、８８０℃近傍で
ＴｉまたはＴｉ合金自体の同業変態が起こるために結晶
構造が変化して、ＴｆまたはＴｉ合金の内部歪が増大し
、またこれに伴う割れ等の問題の発生を回避するためで
あ次に窒化処理時の保持時間を１時間以上と限定した理
由について述べる。Dissociated N atoms diffuse and blow into the Ti or T1 alloy, but the diffusion rate at this time increases with the ambient temperature, so the higher the ambient temperature, the more N atoms diffuse into the surface of the TL or Ti alloy. The depth increases and the surface T
The thickness of the iH film increases. At this time, if the temperature is less than 400°C, the diffusion rate of N atoms into Ti or Ti alloy is extremely low, and the formation of a TiN film is extremely small, so nitriding treatment cannot be performed in practice. . Furthermore, the upper limit was set at 850°C because at around 880°C Ti or Ti alloy itself undergoes a similar transformation, which changes the crystal structure, increases the internal strain of Tf or Ti alloy, and causes cracks and other problems associated with this. The reason why the holding time during the nitriding treatment was limited to one hour or more will be described next, in order to avoid the occurrence of problems.
ＴｉまたはＴ１合金の表面に生成するＴｉＮの皮膜の厚
さは、前述したようにＮＨｌより解離してＴｉまたはＴ
ｉ合金の表面に拡散するＮ原子の数により決定されるの
であるから、拡散時間すなわち保持時間が長ければ長い
ほど、ＴｉＮの皮膜の厚さも増大することになる０本発
明者の知見によれば１時間未満の保持時間ではＮ原子の
拡散深さが擺めて小さく実用上子ＩＮの皮膜が形成され
ないこととなるからである。また保持時間の上限は特に
限定する必要がなく目標とする皮膜の厚さに応じて決定
すればよいことはいうまでもない。As mentioned above, the thickness of the TiN film formed on the surface of Ti or T1 alloy is due to the Ti or T1 alloy dissociating from NH1.
Since it is determined by the number of N atoms diffusing onto the surface of the i-alloy, the longer the diffusion time, that is, the retention time, the thicker the TiN film becomes.According to the findings of the present inventors. This is because, if the holding time is less than 1 hour, the diffusion depth of N atoms will be too small, and in practical terms, a film of IN will not be formed. It goes without saying that the upper limit of the holding time does not need to be particularly limited and may be determined depending on the target thickness of the film.
前述の雰囲気条件を満足する熱処理炉にＴｉまたはＴｉ
合金を挿入して１時間以上、４００〜８５０℃の温度範
囲に加熱・保持することにより容易にかつ確実に窒化処
理することが可能になるのである。Ti or Ti is placed in a heat treatment furnace that satisfies the above atmospheric conditions.
By inserting the alloy and heating and maintaining it at a temperature in the range of 400 to 850° C. for one hour or more, it becomes possible to perform the nitriding process easily and reliably.
ところで本発明において用いる雰囲気においては、ＮＨ
ｓを高温下で解離させるためＮ原子のみならず、Ｈ原子
も発生する。このＨ原子がＴｉまたはＴｉ合金の内部へ
拡散するとＴｉまたはＴｉ合金内にＴｉＬという水素化
物を形成することがある。 ＴＩＨ。By the way, in the atmosphere used in the present invention, NH
Since s is dissociated at high temperature, not only N atoms but also H atoms are generated. When these H atoms diffuse into the Ti or Ti alloy, a hydride called TiL may be formed within the Ti or Ti alloy. T.I.H.
ば脆く、応力等により容易にクランクを発生し、窒化処
理したＴｉまたはＴｉ合金からなる材料にいわゆる水素
脆性をもたらすことがある。よってこのＴｉＨ，の形成
を防ぐには、−旦窒化処理したＴｉまたはＴ１合金から
なる被処理材を不活性ガスの雰囲気中で加熱保持し、水
素をＴｉまたはＴｉ合金からなる被処理材から外部に拡
散させておくことが望ましい、その場合の加５！８温度
、加熱保持時間は特に限定する必要がないが、水素の完
全な除去という観点からは、４００℃以上、１時間以上
であることが望ましい、上記不活性雰囲気としても前述
のようにＮいＡｒガス等のガス雰囲気が例示される。It is brittle, easily cracks due to stress, etc., and may cause so-called hydrogen embrittlement in materials made of nitrided Ti or Ti alloys. Therefore, in order to prevent the formation of TiH, the first nitrided material made of Ti or T1 alloy is heated and maintained in an inert gas atmosphere to remove hydrogen from the material made of Ti or Ti alloy. In that case, there is no need to particularly limit the heating temperature and heating holding time, but from the viewpoint of complete hydrogen removal, the temperature should be 400°C or more and 1 hour or more. The above-mentioned inert atmosphere is preferably a gas atmosphere such as N or Ar gas as described above.
次に本発明を実施例を用いて詳細に説明するが、これは
あくまでも本発明の例示であり、これにより本発明が不
当に制限されろものではない。Next, the present invention will be explained in detail using Examples, but these are merely illustrative of the present invention, and the present invention should not be unduly limited thereby.
（実施例１）
純Ｔｉおよび第１表に成分組成を示すＴ１合金それぞれ
からなる棒塊（直径２３０ａ＋ｍ）を第２表に示す条件
下で窒化処理を行い（ＰＩＩ（３ガスと混合したガスば
Ａｔであった）、冷却後棒塊をＮ２雰囲気の炉内に入れ
て５００℃、１時間加熱保持して試料Ｎｉｌないし試料
磁２０を得た。(Example 1) A rod ingot (diameter 230a+m) made of pure Ti and a T1 alloy whose composition is shown in Table 1 was nitrided under the conditions shown in Table 2 (PII (gas mixture mixed with three gases)). After cooling, the bar ingots were placed in a furnace with an N2 atmosphere and heated and held at 500° C. for 1 hour to obtain Samples Nil to Sample Magnet 20.
第１表
得られた試料について、ＴｉＮ層の厚さをミクロ検鏡で
、表層部硬度（Ｈｖ）をビッカース硬度計で、さらにシ
ャルピー衝撃試験により材料の衝撃特性を調査し、結果
を純Ｔ！、Ｔｉ合金のそれぞれに分けて第２表にまとめ
た。For the samples obtained in Table 1, the thickness of the TiN layer was measured using a microscopic microscope, the surface layer hardness (Hv) was measured using a Vickers hardness tester, and the impact properties of the material were investigated using a Charpy impact test. , Ti alloys are summarized in Table 2.
試料魚１ないし試料阻１２は本発明にかかる方法に得ら
れた窒化処理試料であるが、皮膜の厚さ、皮膜硬度さら
にシャルピー衝撃試験値ともに優れた値を示しており、
本発明にかかる方法により疲労強度、耐食性および靭性
に優れた窒化処理ＴｉまたはＴｉ合金が得られたことが
わかる。Sample fish 1 to sample 12 are nitrided samples obtained by the method according to the present invention, and they show excellent values in film thickness, film hardness, and Charpy impact test value.
It can be seen that a nitrided Ti or Ti alloy with excellent fatigue strength, corrosion resistance, and toughness was obtained by the method according to the present invention.
海洋構造物用材料としての目標とする皮膜厚さ、皮膜硬
度およびシャルピー衝撃試験値はそれぞれ２５４ｓ 、
［ｌｖ ８００．２ｋｇｍであり、本発明にかかる方法
により得られた試料Ｎｌｌないし試料階１２はこれらの
値をすべて満足している。The target film thickness, film hardness, and Charpy impact test value as a material for marine structures are 254 s, respectively.
[lv] is 800.2 kgm, and Samples N11 to 12 obtained by the method according to the present invention satisfy all of these values.
これに対し、試料嵐１３ないし試料磁２０は、比較例の
方法で得た試料である。On the other hand, Sample Arashi 13 to Sample Magnet 20 are samples obtained by the method of the comparative example.
試料Ｎａ１３および試料磁１７は、窒化処理時の雰囲気
中のＮ１．量が１５％と本発明の範囲より少ない条件、
で窒化処理した試料であるが、得られた皮膜の厚さが２
５μ−に達さず、目標とする皮膜特性を有していないた
め、海洋構造物材料として適していないことがわかる。Sample Na13 and sample magnet 17 were exposed to N1. Conditions where the amount is 15%, which is less than the scope of the present invention,
This is a sample nitrided with
It can be seen that it is not suitable as a material for marine structures because it does not reach 5 μ- and does not have the target film characteristics.
また、試料患１４、試料患１５、試料阻１８および試Ｆ
４１’ｋ１９は、窒化処理時の保持時間が０．５時間と
本発明の範囲よりも少ない時間で窒化処理した試料であ
るが、得られた皮膜の厚さが５μ鋼以下となっているた
め実用上耐食性が不足し、やはり目標とする皮膜特性を
有していないため、海洋構造物材料として適していない
ことがわかる。In addition, sample 14, sample 15, sample 18, and sample F
41'k19 is a sample that was nitrided with a holding time of 0.5 hours, which is shorter than the range of the present invention, but the thickness of the obtained film was less than 5μ steel. It can be seen that it is not suitable as a material for marine structures because it lacks practical corrosion resistance and does not have the desired film properties.
また試料阻１６および試料隠２０は、窒化処理時の保持
温度が本発明の範囲より低い条件で窒化処理した試料で
あるが、得られた皮膜の厚さが５μ−以下となり、やは
り目標とする皮膜特性を有していないことがわかる。In addition, although Sample No. 16 and Sample No. 20 were nitrided under conditions in which the holding temperature during nitriding was lower than the range of the present invention, the thickness of the obtained film was 5μ or less, which still meets the target. It can be seen that it does not have film characteristics.
（実施例２）
純Ｔｔおよび第１表に示す組成を有するＴｉ合金からな
る捧塊（直径２３０ ｍ）を５水準の雰囲気（ＮＨｓ量
：２０．４０．６０．８０．１００体積％）中で５００
℃で３時間加熱保持して窒化処理を行って、冷却後被処
理材をＨｚ雰囲気の炉内に入れて５００℃、１時間加熱
保持して試料１１ｍ１ないし試料阻１０を得た。(Example 2) An ingot (diameter 230 m) made of pure Tt and a Ti alloy having the composition shown in Table 1 was prepared in five levels of atmosphere (NHs amount: 20.40.60.80.100% by volume). 500
The material was heated and held at .degree. C. for 3 hours for nitriding treatment, and after cooling, the material to be treated was placed in a furnace in a Hz atmosphere and heated and held at 500.degree. C. for 1 hour to obtain samples 11ml to 10.
得られた試料の皮膜の厚さをミクロ検鏡で、表面硬度を
ビッカース硬度計により測定し結果を第３表にまとめた
。The thickness of the film of the obtained sample was measured using a microscopic microscope, and the surface hardness was measured using a Vickers hardness meter, and the results are summarized in Table 3.
第３表に示す結果から明らかなように
（＋）雰囲気中のＮＨｉガス量が増加するにつれて皮膜
の厚さは増加する
（ ｉｉ ）雰囲気中のＮＨ，ガス量が本発明の範囲内
である２０９Ａ以上であれば、皮膜の硬度は用いる材料
毎に一定であり、極めて高い値を示す
ことがわかる。つまり （ｉ）および（ｉｉ ）より本
発明によって目標とする皮膜およびその厚さを得るには
、雰囲気中のＮＨ３ガス量を調節すればよいことがわか
る。As is clear from the results shown in Table 3, (+) the film thickness increases as the amount of NHi gas in the atmosphere increases (ii) 209A where the amount of NH and gas in the atmosphere is within the range of the present invention If it is above, it can be seen that the hardness of the film is constant depending on the material used and exhibits an extremely high value. In other words, from (i) and (ii) it can be seen that in order to obtain the target film and its thickness according to the present invention, it is sufficient to adjust the amount of NH3 gas in the atmosphere.
（実施例３）
（ｉ）純Ｔ＋および第１表に示す成分組成を有するＴｉ
合金からなる棒塊（直径２３０ ｆｉ）を雰囲気温度５
００℃、ＮＨ３ガスＷｔ６０体積％および処理時間を４
水準（３，５、ＩＯ２３０時間）として窒化処理した時
の表面皮膜の厚さと窒化処理時間の関係を第１図に、ま
た
（ｉｉ）ＮＨｚガス量６０体積％、処理時間３時間およ
び雰囲気温度を４水準（５００，６００，７００，８０
０℃）として窒化処理した時の表面皮膜の厚さと゛望イ
φ処理温度の関係を第２図に示す。(Example 3) (i) Pure T+ and Ti having the component composition shown in Table 1
A bar block (diameter 230 fi) made of an alloy is heated to an ambient temperature of 5.
00℃, NH3 gas Wt 60% by volume and treatment time 4
Figure 1 shows the relationship between the thickness of the surface film and the nitriding time when nitriding was performed at levels (3, 5, IO230 hours), and (ii) the NHz gas amount was 60% by volume, the treatment time was 3 hours, and the ambient temperature was 4 levels (500, 600, 700, 80
FIG. 2 shows the relationship between the thickness of the surface film when nitriding is performed at a temperature of 0° C. and the desired φ treatment temperature.
第１図または第２図より明らかなように、本発明により
生成皮膜の厚さは、窒化処理時間または窒化処理温度を
決定することにより、容易にかつ確実に所望の値とする
ことが出来ることがわかる。As is clear from FIG. 1 or 2, the thickness of the film produced according to the present invention can be easily and reliably set to a desired value by determining the nitriding treatment time or nitriding treatment temperature. I understand.
（発明の効果）
以上詳述してきたように、本発明は、ＴｉまたはＴｉ合
金からなる被処理材を、特に被処理材が大型であっても
、特定した体積％のＮＨ２ガスの雰囲気中で、特定した
温度域および時間で加熱・保持することとしたため、特
別なチャンバーを必要とせず容易にかつ確実にＴｔまた
はＴｉ合金からなる材料の表面の窒化処理を行うことが
可能となった。また本発明で用いる窒化処理温度は、Ｔ
ｔまたはＴｉ合金の焼鈍温度に近（、窒化処理と焼鈍と
を併せて実施できるという効果もある。かかる効果を有
する本発明の実用上の意義は著しい。(Effects of the Invention) As described in detail above, the present invention enables processing of a material to be treated made of Ti or a Ti alloy in an atmosphere of NH2 gas of a specified volume percent, even if the material to be treated is particularly large. By heating and holding in a specified temperature range and for a specified time, it became possible to easily and reliably perform nitriding treatment on the surface of a material made of Tt or Ti alloy without the need for a special chamber. Further, the nitriding temperature used in the present invention is T
There is also the effect that nitriding treatment and annealing can be carried out together at temperatures close to the annealing temperature of Ti or Ti alloys.The practical significance of the present invention having such an effect is significant.
第１図は、本発明にかかる方法により生成するＴｉＮ皮
膜の厚さに及ぼす処理時間の関係をあられすグラフ；
第３図は、従来法であるイオン注入法において用いるイ
オン注入装置の概略図；および第４図は、従来法である
イオン窒化法において用いるイオン窒化装置の概略図で
ある。
ネ１
図FIG. 1 is a graph showing the relationship between the processing time and the thickness of the TiN film produced by the method according to the present invention; FIG. 3 is a schematic diagram of an ion implantation apparatus used in the conventional ion implantation method; FIG. 4 is a schematic diagram of an ion nitriding apparatus used in the conventional ion nitriding method. Figure 1
Claims (2)
して、 ＮＨ＿３ガス：２０体積％以上１００体積％未満残部不
活性ガスである雰囲気中かまたはＮＨ＿３ガス：１００
体積％ である雰囲気中で、４００℃以上８５０℃以下の温度範
囲で１時間以上加熱・保持することを特徴とする、Ｔｉ
またはＴｉ合金の窒化処理法。(1) When nitriding the surface of Ti or Ti alloy, NH_3 gas: 20% by volume or more and less than 100% by volume in an atmosphere where the balance is an inert gas or NH_3 gas: 100% by volume.
% by volume, heating and holding in a temperature range of 400°C or more and 850°C or less for 1 hour or more.
Or Ti alloy nitriding method.
引き続き不活性ガスの雰囲気中で加熱保持することを特
徴とする、ＴｉまたはＴｉ合金の窒化処理法。(2) A method for nitriding Ti or Ti alloy, characterized in that the material to be treated obtained by the nitriding method according to claim 1 is subsequently heated and held in an inert gas atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174600A JPH0663081B2 (en) | 1988-07-13 | 1988-07-13 | Ni or Ti alloy nitriding method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174600A JPH0663081B2 (en) | 1988-07-13 | 1988-07-13 | Ni or Ti alloy nitriding method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0225559A true JPH0225559A (en) | 1990-01-29 |
| JPH0663081B2 JPH0663081B2 (en) | 1994-08-17 |
Family
ID=15981409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63174600A Expired - Lifetime JPH0663081B2 (en) | 1988-07-13 | 1988-07-13 | Ni or Ti alloy nitriding method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0663081B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002080958A (en) * | 2000-09-11 | 2002-03-22 | Kiyotaka Matsuura | Method for forming carbonitride layer on surface of metallic material and titanium based metallic material provided with carbonitride layer on surface |
| KR100594998B1 (en) * | 2004-05-14 | 2006-06-30 | 주식회사 케이피티 | Method for nitriding of Ti and Ti alloy |
| US20100210117A1 (en) * | 2009-02-13 | 2010-08-19 | Asm International N.V. | Selective removal of oxygen from metal-containing materials |
| US9127340B2 (en) | 2009-02-13 | 2015-09-08 | Asm International N.V. | Selective oxidation process |
| WO2022184812A1 (en) * | 2021-03-03 | 2022-09-09 | Elos Medtech Pinol A/S | Surface hardening of group iv metals |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5060437A (en) * | 1973-10-01 | 1975-05-24 | ||
| JPS5060438A (en) * | 1973-10-01 | 1975-05-24 |
-
1988
- 1988-07-13 JP JP63174600A patent/JPH0663081B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5060437A (en) * | 1973-10-01 | 1975-05-24 | ||
| JPS5060438A (en) * | 1973-10-01 | 1975-05-24 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002080958A (en) * | 2000-09-11 | 2002-03-22 | Kiyotaka Matsuura | Method for forming carbonitride layer on surface of metallic material and titanium based metallic material provided with carbonitride layer on surface |
| JP4641091B2 (en) * | 2000-09-11 | 2011-03-02 | 清隆 松浦 | Method of forming carbonitride layer on metal material surface and titanium-based metal material having carbonitride layer on surface |
| KR100594998B1 (en) * | 2004-05-14 | 2006-06-30 | 주식회사 케이피티 | Method for nitriding of Ti and Ti alloy |
| US20100210117A1 (en) * | 2009-02-13 | 2010-08-19 | Asm International N.V. | Selective removal of oxygen from metal-containing materials |
| US8889565B2 (en) * | 2009-02-13 | 2014-11-18 | Asm International N.V. | Selective removal of oxygen from metal-containing materials |
| US9127340B2 (en) | 2009-02-13 | 2015-09-08 | Asm International N.V. | Selective oxidation process |
| WO2022184812A1 (en) * | 2021-03-03 | 2022-09-09 | Elos Medtech Pinol A/S | Surface hardening of group iv metals |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0663081B2 (en) | 1994-08-17 |
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