JPH08134570A - Composite material having high corrosion resistance and wear resistance - Google Patents
Composite material having high corrosion resistance and wear resistanceInfo
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- JPH08134570A JPH08134570A JP30269494A JP30269494A JPH08134570A JP H08134570 A JPH08134570 A JP H08134570A JP 30269494 A JP30269494 A JP 30269494A JP 30269494 A JP30269494 A JP 30269494A JP H08134570 A JPH08134570 A JP H08134570A
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- resistance
- wear
- corrosion resistance
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、高耐食性、高耐摩性
の炭化物およびほう化物、さらに所望により窒化物を主
体とする硬質相を、Ｎｉ基マトリックスで結合した高耐
食耐摩耗複合材料に関するものである。例えば、腐食性
の強いプラスチックやゴム等の可塑物を対象とする樹脂
加工機械用のシリンダ材やスクリュ材に適しており、特
に、塩酸、弗化水素酸に対する耐食性を必要とし、か
つ、耐摩耗性を要求されるコンパウンド用樹脂加工機械
用の耐食耐摩耗材に好適である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high corrosion resistance and wear resistance composite material in which a hard phase mainly composed of carbides and borides having a high corrosion resistance and a high wear resistance, and optionally a nitride is bonded by a Ni-based matrix. Is. For example, it is suitable for cylinder materials and screw materials for resin processing machines that target highly corrosive plastics and plastics such as rubber. In particular, corrosion resistance to hydrochloric acid and hydrofluoric acid is required, and abrasion resistance is also required. It is suitable as a corrosion resistant and abrasion resistant material for resin processing machines for compounds that require high properties.
【０００２】[0002]
【従来の技術】樹脂加工機械における押出機や射出機の
シリンダ、スクリュ材は、加工対象物による摩耗を受け
たり、金属間の接触摩耗を受け易いので、耐摩耗性に優
れた材料で構成する必要がある。このため従来は、上記
材料に、耐摩耗性に優れた自溶性耐摩耗Ｎｉ基合金やＮ
ｉ基自溶性合金にＷＣのような硬質粒子を添加した複合
材料が使用されている。2. Description of the Related Art Cylinders and screw materials of an extruder or an injection machine in a resin processing machine are liable to be worn by an object to be processed or contact wear between metals, and are therefore made of materials having excellent wear resistance. There is a need. For this reason, conventionally, the above materials have been used in addition to the self-fluxing wear-resistant Ni-based alloys and N having excellent wear resistance.
A composite material in which hard particles such as WC are added to an i-based self-fluxing alloy is used.
【０００３】[0003]
【発明が解決しようとする課題】ところで、最近の成形
材料の高機能化により、樹脂加工機械が使用される環境
はより過酷になっており、例えば、高温条件下での成形
加工において、樹脂加工機械は、樹脂から発生する腐食
ガスにさらされ、腐食を受け易い状態になる。したがっ
て、従来のように、樹脂加工機械用の材料についても、
耐摩耗性だけを重視することはできず、耐食性について
も優れた特性が要求されている。しかし、前記した自溶
性耐摩耗Ｎｉ基合金、ＷＣ添加複合材料は、耐摩耗性は
良好であるが、耐食性は十分ではない。これに対し、耐
食性に優れた材料としては、Ｎｉ−Ｃｒ−Ｍｏ合金が知
られており、実際に、樹脂加工機械への使用例もある。
しかし、この材料は、耐摩耗性が十分ではなく、例え
ば、部材同士の接触による凝着やカジリを生じ易いとい
う欠点がある。以上のように、従来材においては、耐食
性に優れた材料は耐摩耗性が十分でなく、また、耐摩耗
性に優れた材料は耐食性が不十分である。このため最近
では、耐摩耗性、耐食性のいずれにも優れた特性を有す
る材料の開発が進められているが、両方の優れた特性を
十分に合わせもつ材料の実現は達成されていない。この
発明は、上記事情を背景としてなされたものであり、使
用される条件の厳しい樹脂加工機械における高腐食環境
下での使用にも耐え得る、高耐食耐摩耗性複合材料を提
供することを目的とする。By the way, due to the recent enhancement of the functionality of molding materials, the environment in which a resin processing machine is used has become more severe. For example, in molding processing under high temperature conditions, resin processing The machine is exposed to the corrosive gases generated by the resin and is susceptible to corrosion. Therefore, even with conventional materials for resin processing machines,
It is not possible to focus only on wear resistance, and excellent characteristics are also required for corrosion resistance. However, although the self-fluxing wear-resistant Ni-based alloy and the WC-added composite material described above have good wear resistance, they do not have sufficient corrosion resistance. On the other hand, a Ni-Cr-Mo alloy is known as a material having excellent corrosion resistance, and in fact, there is an example of use in a resin processing machine.
However, this material does not have sufficient abrasion resistance, and has a drawback that, for example, adhesion or galling due to contact between members is likely to occur. As described above, in the conventional materials, the material excellent in corrosion resistance does not have sufficient wear resistance, and the material excellent in wear resistance has insufficient corrosion resistance. For this reason, recently, development of materials having excellent properties in both wear resistance and corrosion resistance has been advanced, but realization of a material sufficiently combining both excellent properties has not been achieved. The present invention has been made in view of the above circumstances, and an object thereof is to provide a highly corrosion-resistant and abrasion-resistant composite material that can withstand use in a highly corrosive environment in a resin processing machine under severe conditions of use. And
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
本願発明者らはＭｏ−Ｃｒ−Ｎｉ系のほう化物を主体と
する硬質相と、ＷＣ、ＴｉＣ、ＴｉＮ、ＴａＣなどの炭
化物や窒化物を分散させた硬質の合金に着目した。さら
に、本発明者らは、耐食性を具備した耐摩耗材料の開発
過程において、このほう化物が高い硬さを持つだけでな
く、優れた耐食性を有することを見いだし、上記したほ
う化物、ＷＣ、ＴｉＣ、ＴｉＮ、ＴａＣなどの炭化物や
窒化物、Ｎｉ基合金の組合わせにより、耐食性、耐摩耗
性ともに優れた本発明の複合材料を得たものである。In order to solve the above problems, the inventors of the present invention have a hard phase mainly composed of Mo-Cr-Ni-based borides and carbides and nitrides such as WC, TiC, TiN and TaC. Attention was paid to a hard alloy in which is dispersed. Furthermore, the present inventors have found that, in the process of developing a wear resistant material having corrosion resistance, this boride has not only high hardness but also excellent corrosion resistance, and the above boride, WC, TiC A composite material of the present invention having excellent corrosion resistance and wear resistance is obtained by combining a carbide or a nitride such as TiN, TiN or TaC, or a Ni-based alloy.
【０００５】すなわち、本願発明のうち第１の発明の高
耐食耐摩耗性複合材料は、炭化物およびほう化物を主体
とする硬質相がＮｉ基マトリックスで結合された複合材
料であって、前記マトリックスおよび硬質層は、総量で
Ｂ：２〜６重量％、Ｃｒ：２１〜３８重量％、Ｍｏ：８
〜２２重量％、Ｗ：０．５〜１２重量％、Ｆｅ：３〜６
重量％、Ｃ：０．４〜３重量％、Ｃｕ：０〜２重量％を
含有し、さらにＴｉ：２〜２０重量％、Ｔａ：１〜５重
量％の１種または２種を含有し、残部がＮｉ及び不可避
的不純物よりなることを特徴とする。第２の発明は、Ｎ
ｉ基マトリックスに、炭化物、ほう化物および窒化物を
主体とする硬質層が分散した複合材料であって、前記マ
トリックスおよび硬質層は、総量でＢ：２〜６重量％、
Ｃｒ：２１〜３８重量％、Ｍｏ：８〜２２重量％、Ｗ：
０．５〜１２重量％、Ｆｅ：３〜６重量％、Ｃ：０．４
〜３重量％、Ｎ：３重量％以下、Ｃｕ：０〜２重量％を
含有し、さらに、Ｔｉ：２〜２０重量％、Ｔａ：１〜５
重量％の１種または２種を含有し、残部がＮｉ及び不可
避的不純物よりなることを特徴とする。第３の発明は、
第１又は第２の発明において、硬質層中のＷ、Ｔｉ、Ｔ
ａの合計含有量が６〜２５％であることを特徴とする。That is, the high corrosion-resisting and abrasion-resistant composite material of the first invention of the present invention is a composite material in which a hard phase mainly composed of carbide and boride is bonded by a Ni-based matrix, and the matrix and The total amount of the hard layer is B: 2 to 6% by weight, Cr: 21 to 38% by weight, Mo: 8
-22% by weight, W: 0.5-12% by weight, Fe: 3-6
%, C: 0.4 to 3% by weight, Cu: 0 to 2% by weight, Ti: 2 to 20% by weight, Ta: 1 to 5% by weight, and 1 or 2 types thereof, The balance consists of Ni and inevitable impurities. The second invention is N
A composite material in which a hard layer mainly composed of carbide, boride and nitride is dispersed in an i-based matrix, wherein the matrix and the hard layer are B: 2 to 6% by weight in total,
Cr: 21-38% by weight, Mo: 8-22% by weight, W:
0.5 to 12% by weight, Fe: 3 to 6% by weight, C: 0.4
˜3% by weight, N: 3% by weight or less, Cu: 0 to 2% by weight, further Ti: 2 to 20% by weight, Ta: 1 to 5
It is characterized by containing 1% or 2% by weight and the balance being Ni and inevitable impurities. The third invention is
1st or 2nd invention WHEREIN: W, Ti, T in a hard layer
The total content of a is 6 to 25%.
【０００６】上記硬質相では、添加合金のままの炭化
物、窒化物、ほう化物、または含有成分と反応した炭化
物、窒化物、ほう化物が主体となっており、ほう化物の
多くは複合ほう化物からなる。また、炭化物や窒化物に
おいても、複合炭化物や複合窒化物が生成される場合が
ある。なお、本発明における組成物は粉末として提供
し、これを焼結する粉末冶金法により製造するのが望ま
しく、この方法によれば、硬質物が均一に分散した複合
材料が得られる。さらに、ＨＩＰ法を用いることによ
り、より高強度、高靱性の複合材料が得られる。In the above hard phase, carbides, nitrides, borides as the added alloy, or carbides, nitrides, borides reacted with the contained components are the main components, and most of the borides are compound borides. Become. Further, in carbides and nitrides, compound carbides and nitrides may be produced. The composition of the present invention is preferably provided as a powder and manufactured by a powder metallurgy method of sintering the powder. According to this method, a composite material in which hard materials are uniformly dispersed can be obtained. Further, by using the HIP method, a composite material having higher strength and higher toughness can be obtained.
【０００７】上記粉末冶金において、Ｗ、Ｔｉ、Ｔａの
全部または一部をＷＣ等の炭化物粉末として提供し、Ｃ
ｒ、Ｍｏ、Ｂの全部または一部をＣｒＢ、ＭｏＢ粉末と
して提供し、さらにＴｉ等の窒化物を粉末として提供す
ることができる。これらは、例えば、ＷＣ：５〜１５重
量％、ＴｉＣ：３〜１５重量％、ＴａＣ：０〜５重量
％、ＣｒＢ：０〜２４．５重量％、ＭｏＢ：０〜２４．
５重量％、ＴｉＮ：０〜１３重量％で示すことができ
る。これら粉末を用いた場合に、母合金粉末は、発明の
範囲内において必要に応じた組成を有するものが使用さ
れる。例えば、Ｃｒ：１５〜１６重量％、Ｍｏ：１５〜
１７重量％、Ｗ：３〜４重量％で残部が実質的にＮｉか
らなる母合金が使用される。In the above powder metallurgy, all or part of W, Ti and Ta is provided as a carbide powder such as WC, and C
All or part of r, Mo, and B can be provided as CrB and MoB powders, and nitrides such as Ti can be provided as powders. These are, for example, WC: 5 to 15% by weight, TiC: 3 to 15% by weight, TaC: 0 to 5% by weight, CrB: 0 to 24.5% by weight, MoB: 0 to 24.
5% by weight, TiN: 0 to 13% by weight. When these powders are used, as the master alloy powder, those having a composition as required within the scope of the invention are used. For example, Cr: 15 to 16% by weight, Mo: 15 to 15
A master alloy of 17% by weight, W: 3 to 4% by weight and the balance substantially consisting of Ni is used.
【０００８】上記母合金粉末は、焼結性、組織の均一性
のためにアトマイズ法で製造するのが望ましい。炭化物
粉末、窒化物粉末、ほう化物粉末、母合金粉末は、ボー
ルミルなどによって所定量を混合し、この混合粉を成形
した後、焼結する。例えば液相焼結によって行う場合に
は、１０００〜１３００℃で１０〜１２０分間焼結す
る。なお、焼結方法はこれに限定されるものではなく、
普通焼結法の他に熱間等方圧加圧法（ＨＩＰ）、ホット
プレス法などの他の焼結法を採用することも可能であ
る。 また、焼結温度を高くして、例えば１１００℃以
上で焼結する場合にはＣｒＢは、他の成分と相互に反応
してそれぞれ複合ほう化物を生成する。また、熱力学的
に安定なＴｉＣなどは反応せずに単体で組織中に分散す
る。また、ＷＣのように部分的に反応する炭化物が存在
し、それぞれの特性を示す。なお、本発明は、前述した
ように樹脂加工機械やさらにセラミックス、金属等の押
出成形機あるいは射出成形機等のシリンダ材やスクリュ
材等に適しているが、これらの用途に限定されるもので
はなく、その他に耐食耐摩耗性を要求される用途の材料
として使用することができる。The above master alloy powder is preferably manufactured by the atomizing method for the sake of sinterability and uniformity of structure. The carbide powder, the nitride powder, the boride powder, and the master alloy powder are mixed in a predetermined amount by a ball mill or the like, and the mixed powder is molded and then sintered. For example, when liquid phase sintering is performed, the sintering is performed at 1000 to 1300 ° C. for 10 to 120 minutes. The sintering method is not limited to this,
Besides the normal sintering method, it is also possible to adopt other sintering methods such as hot isostatic pressing (HIP) and hot pressing. In addition, when the sintering temperature is raised and, for example, sintering is performed at 1100 ° C. or higher, CrB reacts with other components to form a compound boride. In addition, thermodynamically stable TiC or the like does not react and disperses alone in the tissue. In addition, there are partially reactive carbides such as WC, which exhibit their respective characteristics. As described above, the present invention is suitable for a cylinder material, a screw material, and the like of a resin processing machine and an extrusion molding machine or an injection molding machine of ceramics, metal, etc., but is not limited to these applications. In addition, it can be used as a material for other applications requiring corrosion resistance and abrasion resistance.
【０００９】[0009]
【作用】すなわち、本願発明の複合材料よれば、各種実
験の結果、摺動時に、Ｃｒ、Ｍｏ、Ｗ等で構成されたほ
う化物（主として複合ほう化物）が潤滑材の役割を果た
し、相手材に対する攻撃性を緩和する。また、複合ほう
化物は、適度な耐摩耗性を発揮するとともに、耐食性を
向上させる。さらに、複合ほう化物にＷ、Ｔｉ、Ｔａ等
で構成される炭化物あるいはＴｉＮ等の窒化物を組み合
わせることにより、金属同士の凝着摩耗を軽減し、かつ
高硬度である炭化物や窒化物のもつ自身の耐摩耗性によ
りアブレシブ摩耗に対しても有効に作用する。したがっ
て、本願発明により、耐食性、耐摩耗性の両特性が十分
に優れている材料が得られる。次いで、本発明の成分の
作用および含有量（重量％）の限定理由を述べる。That is, according to the composite material of the present invention, as a result of various experiments, during sliding, the boride composed of Cr, Mo, W, etc. (mainly the composite boride) plays the role of the lubricant, and Mitigates aggression against. In addition, the composite boride exhibits appropriate wear resistance and improves corrosion resistance. Furthermore, by combining a compound boride with a carbide composed of W, Ti, Ta, etc., or a nitride such as TiN, the adhesion wear between metals is reduced, and the carbide or nitride with high hardness itself It also effectively works against abrasive wear due to its wear resistance. Therefore, according to the present invention, a material having both excellent corrosion resistance and abrasion resistance can be obtained. Next, the action of the components of the present invention and the reasons for limiting the content (% by weight) will be described.
【００１０】Ｂは、Ｃｒ、Ｍｏ等と反応して硬質相とな
るＭ3Ｂ2型の複合ほう化物（電子線マイクロアナライザ
ー（ＥＰＭＡ）による面分析、Ｘ線回折による調査で結
果確認）を形成するために、必要不可欠な元素である。
ただし、Ｂ含有量が２重量％未満になると耐摩耗性が悪
くなり、一方、６重量％を越えると硬質相の量が過多と
なり、強度の低下が生じるため、含有量を２〜６重量％
とする。なお、同様の理由で２〜４重量％とするのが望
ましい。B forms a M 3 B 2 type complex boride (a surface analysis by an electron beam microanalyzer (EPMA) and a result confirmed by an examination by X-ray diffraction) which becomes a hard phase by reacting with Cr, Mo, etc. It is an indispensable element in order to do.
However, if the B content is less than 2% by weight, the wear resistance becomes poor, while if it exceeds 6% by weight, the amount of the hard phase becomes excessive and the strength decreases, so the content is 2 to 6% by weight.
And For the same reason, it is desirable that the amount is 2 to 4% by weight.
【００１１】Ｃｒは、焼結時に反応して炭化物を生成し
たり、ほう化物として硬質相を構成するだけでなく、結
合相にも固溶して、耐食性、耐摩耗性、耐熱性、耐酸化
性を向上させる働きを持つ。主として、ほう化物として
供給したり、母材合金成分として含有させる。その含有
量が２１重量％未満では、耐食性が不十分であり、ま
た、３８重量％を越えると、含有量に見合った耐食性の
向上が認められず、また、靱性も低下するため２１〜３
８重量％に限定する必要がある。さらに同様の理由で２
２〜２８重量％とするのが望ましい。[0011] Cr not only forms a carbide by reacting during sintering or forms a hard phase as a boride, but also forms a solid solution in the binder phase, so that it has corrosion resistance, wear resistance, heat resistance, and oxidation resistance. It has a function to improve sex. Mainly supplied as a boride or contained as a base alloy component. If the content is less than 21% by weight, the corrosion resistance is insufficient, and if it exceeds 38% by weight, the improvement in the corrosion resistance commensurate with the content is not recognized, and the toughness is also lowered, so that it is 21 to 3%.
It should be limited to 8% by weight. For the same reason, 2
It is desirable that the amount is 2 to 28% by weight.
【００１２】Ｍｏは、Ｂと反応して複合ほう化物を生成
し、弗化水素酸などの還元性雰囲気に対する腐食抵抗を
増大させる作用がある。ただし、十分な耐食性を確保す
るために、８重量％以上の含有が必要である。しかし、
２２重量％を越えると、脆弱な金属間化合物を形成し、
耐摩耗性の低下をもたらすので８〜２２重量％に限定す
る。また、同様の理由で１０〜２０重量％とするのが望
ましい。[0012] Mo reacts with B to form a complex boride and has an action of increasing the corrosion resistance to a reducing atmosphere such as hydrofluoric acid. However, in order to secure sufficient corrosion resistance, the content of 8% by weight or more is necessary. But,
If it exceeds 22% by weight, a brittle intermetallic compound is formed,
Since it causes a decrease in wear resistance, it is limited to 8 to 22% by weight. For the same reason, it is desirable to set the content to 10 to 20% by weight.
【００１３】Ｗは、Ｎｉ基合金に分散させる硬質相を構
成させたり、耐熱性を付与するもので、他成分との反応
によって複合炭化物や複合ほう化物を構成するので、炭
化物として供給したり、母材の合金成分として含有させ
る。その含有量は、０．５重量％未満では耐摩耗性の付
与が不十分となり、また、１２重量％を越えると、材料
強度が低下したり、合金の比重が大きくなって高重量化
につながり、部材の構成上不利であるので、０．５〜１
２重量％の範囲とする。W is a component that forms a hard phase to be dispersed in a Ni-based alloy and imparts heat resistance. Since W forms a complex carbide or complex boride by reacting with other components, it is supplied as a carbide. It is contained as an alloy component of the base material. If the content is less than 0.5% by weight, the wear resistance is insufficiently imparted, and if it exceeds 12% by weight, the material strength decreases and the specific gravity of the alloy increases, leading to higher weight. , 0.5-1 because it is disadvantageous in the structure of the member
The range is 2% by weight.
【００１４】Ｔｉ、Ｔａは、Ｗと同様にＮｉ基合金に分
散させる硬質相を構成させるものであり、Ｗは他成分と
の反応によって複合炭化物や複合ほう化物を生成して、
耐摩耗性を向上させるが、Ｔｉ、Ｔａは、炭化物の状態
で供給された場合に、他成分とあまり反応せずに、硬質
炭化物として残存し、耐摩耗性、特に耐アブレシブ摩耗
性を向上させる。これらの作用を確実に得るためにはＴ
ｉ、Ｔａは、炭化物の状態で原料として供給するのが望
ましく、また、Ｔｉの一部は窒化物として供給すること
もできる。ただし、Ｔｉ、Ｔａの含有量が下限未満であ
ると、上記の作用が十分に得られず、一方、上限を超え
ると、材料強度が劣化するため、Ｔｉ：２〜２０重量
％、Ｔａ：１〜５重量％とする。これらＴｉ、Ｔａと前
記したＷとを組み合わせて含有させることにより、耐摩
耗性と耐アブレシブ摩耗性の両方を向上させることがで
きる。但し、これらの成分の合計含有量が、６重量％未
満であると耐摩耗性の付与が不十分となり、また、２５
重量％を越えると、材料強度が劣化するため、合計で６
〜２５重量％に限定するのが望ましい。なお、同様の理
由で、さらに８〜２０重量％に限定するのが望ましく、
また１０〜１５重量％に限定するのが一層望ましい。Ti and Ta constitute a hard phase to be dispersed in a Ni-based alloy like W, and W reacts with other components to form a composite carbide or a boride.
Improves wear resistance, but Ti and Ta, when supplied in the state of carbides, do not react much with other components and remain as hard carbides, improving wear resistance, especially abrasive wear resistance. . To ensure these effects, T
It is desirable that i and Ta be supplied in the form of carbides as raw materials, and part of Ti can also be supplied as nitrides. However, if the content of Ti or Ta is less than the lower limit, the above-mentioned action cannot be sufficiently obtained, while if it exceeds the upper limit, the material strength is deteriorated, so Ti: 2 to 20 wt%, Ta: 1 Up to 5% by weight. By incorporating Ti and Ta in combination with W described above, both the wear resistance and the abrasive wear resistance can be improved. However, if the total content of these components is less than 6% by weight, the abrasion resistance is insufficiently imparted, and
If the weight percentage is exceeded, the strength of the material will deteriorate, so a total of 6
It is desirable to limit it to -25% by weight. For the same reason, it is desirable to further limit the content to 8 to 20% by weight,
It is more desirable to limit the amount to 10 to 15% by weight.
【００１５】ＣとＮは、Ｔｉの炭化物および窒化物と同
様にＮｉ基合金に分散させる硬質相を構成させるもの
で、Ｃｒ、Ｗ等と反応して炭化物や窒化物を形成し、耐
摩耗性の向上に寄与する。その含有量は、０．４重量％
未満では耐摩耗性向上が不十分であり、一方、３重量％
を越えると、炭化物や窒化物が過度となり、相手材攻撃
性が増すとともに機械的特性を損なうので、０．４〜３
重量％に限定する。ただし、硬質層として炭化物を添加
した場合は、炭化物で耐摩耗性が確保されるので、Ｎ含
有量は０〜３重量％の範囲とする。C and N constitute a hard phase to be dispersed in a Ni-based alloy like Ti carbides and nitrides, and react with Cr, W, etc. to form carbides and nitrides, and wear resistance. Contribute to the improvement of. Its content is 0.4% by weight
If the amount is less than 3, abrasion resistance is insufficiently improved, while 3% by weight
If it exceeds 1.0, carbides and nitrides become excessive, the attacking property of the mating material increases and the mechanical properties are impaired.
Limit to wt%. However, when carbide is added as the hard layer, wear resistance is secured by the carbide, so the N content is set to the range of 0 to 3% by weight.
【００１６】Ｆｅは、低温における強度を向上させるた
めに添加する。ただし、３重量％未満では、その作用は
不十分であり、また、６重量％を越えると、耐食性が低
下するので、３〜６重量％に限定する。Fe is added to improve strength at low temperatures. However, if it is less than 3% by weight, the action is insufficient, and if it exceeds 6% by weight, the corrosion resistance decreases, so the content is limited to 3 to 6% by weight.
【００１７】Ｃｕは、Ｎｉ−Ｃｕ合金であるモネル合金
（商標名）に代表されるように、Ｎｉ基合金の耐食性の
向上に寄与するので、所望により含有させる。ただし、
十分な耐食性を得るためには０．５重量％以上含有させ
るのが望ましい。一方、添加量が多くなると合金が軟化
して耐摩耗性が悪くなるので、含有量は２重量％以下と
した。なお、耐摩耗性を重視する場合には無添加とす
る。Since Cu contributes to the improvement of the corrosion resistance of the Ni-based alloy, as represented by Monel alloy (trade name) which is a Ni-Cu alloy, Cu is contained if desired. However,
In order to obtain sufficient corrosion resistance, it is desirable to contain 0.5% by weight or more. On the other hand, when the addition amount is large, the alloy is softened and wear resistance is deteriorated, so the content is set to 2% by weight or less. When the wear resistance is important, no addition is made.
【００１８】Ｎｉは、耐食性の向上に効果のある元素で
あり、Ｂとともに硬質のほう化物を形成して耐摩耗性を
向上させる効果があるので、残部をＮｉとした。なお、
残部のＮｉには不可避的不純物が存在するが、それら
は、本発明の効果を損なわない範囲内で許容される。Ni is an element effective in improving the corrosion resistance and has the effect of forming a hard boride together with B to improve the wear resistance. Therefore, the balance is Ni. In addition,
The balance Ni contains unavoidable impurities, but they are acceptable within a range that does not impair the effects of the present invention.
【００１９】[0019]
【実施例】以下に、この発明の実施例を、比較例（従来
例）と比較しつつ説明する。なお、以下の説明では、成
分量はすべて重量％で示す。まず、表１に示す組成のＮ
ｉ基合金（合金Ａ）を原料粉末の一部として用意し、さ
らに表２に示す成分比で各粉末を秤量して配合し、試験
用混合粉末をそれぞれ調整した。なお、各原料粉末の粒
径は以下に示すとおりである。 （粒径） 合金Ａ：１０〜４４μｍ ＣｒＢ：９μｍ（平均粒径） Ｃｕ ：４４μｍ以下 ＷＣ ：１．９μｍ（平均粒径） ＴｉＣ：１４８μｍ（平均粒径） ＴａＣ：２μｍ（平均粒径） ＴｉＮ：１．１８μｍ（平均粒径）EXAMPLES Examples of the present invention will be described below in comparison with comparative examples (conventional examples). In addition, in the following description, all component amounts are shown by weight%. First, N having the composition shown in Table 1
An i-based alloy (alloy A) was prepared as a part of the raw material powder, and the powders were weighed and mixed in the component ratios shown in Table 2 to prepare respective test mixed powders. The particle size of each raw material powder is as shown below. (Particle size) Alloy A: 10 to 44 μm CrB: 9 μm (average particle size) Cu: 44 μm or less WC: 1.9 μm (average particle size) TiC: 148 μm (average particle size) TaC: 2 μm (average particle size) TiN: 1.18 μm (average particle size)
【００２０】各混合粉末には、さらにパラフィン等のバ
インダを所定量加え、有機溶媒中でボールミルによって
２４時間湿式混合した後、乾燥して２５０〜５００μｍ
の粒径に造粒した。この造粒粉をＣＩＰ等で成形した。
得られた成形体を不活性ガス雰囲気下において、３５０
〜５００℃で２〜４時間加熱して脱脂を行った。そして
脱脂後の成形体を、真空雰囲気下で焼結した。具体的に
は、１０-3Ｔｏｒｒ以下の雰囲気下において、１０００
℃で１時間保持し、さらに、１１８０〜１３５０℃で３
０〜１２０分保持して本発明の焼結体を得た。さらに、
この焼結体を切断加工して、所定形状の試験片（実施例
１〜１０）を製作した。 また、比較のために従来材か
らなる試験片（比較例１、２）を用意した。比較材１
は、市販のＮｉ基耐食合金からなり、比較例２はＮｉ基
自溶性合金からなるものである。なお、実施例１〜１０
及び比較材１、２の成分の総量を表３に示す。上記試験
片のうち、実施例９について、ＥＰＭＡによって面分析
組織観察を行ったところ図１の写真に示すように、マト
リックスとしてＮｉ−Ｆｅ−Ｃｕ−Ｃｒの組成物が形成
されており、硬質相としてはＴｉＣ炭化物とＣｒ−Ｍｏ
−Ｗ−Ｂよりなる複合ほう化物が生成されていた。A predetermined amount of a binder such as paraffin is further added to each mixed powder, and the mixture is wet-mixed in an organic solvent by a ball mill for 24 hours, and then dried to 250 to 500 μm.
Granulated to a particle size of. This granulated powder was molded by CIP or the like.
The obtained molded body is heated under an inert gas atmosphere at 350
Degreasing was performed by heating at ~ 500 ° C for 2 to 4 hours. Then, the degreased compact was sintered in a vacuum atmosphere. Specifically, in an atmosphere of 10 −3 Torr or less, 1000
Hold at ℃ for 1 hour, then at 1180 ~ 1350 ℃ 3
Hold for 0 to 120 minutes to obtain a sintered body of the present invention. further,
This sintered body was cut and processed to prepare test pieces having a predetermined shape (Examples 1 to 10). For comparison, test pieces (Comparative Examples 1 and 2) made of conventional materials were prepared. Comparative material 1
Is a commercially available Ni-based corrosion resistant alloy, and Comparative Example 2 is a Ni-based self-fluxing alloy. In addition, Examples 1-10
Table 3 shows the total amounts of the components of Comparative Materials 1 and 2. Of the above-mentioned test pieces, Example 9 was subjected to area analysis structure observation by EPMA, and as shown in the photograph of FIG. 1, a composition of Ni—Fe—Cu—Cr was formed as a matrix, and the hard phase As TiC carbide and Cr-Mo
A complex boride of -WB was produced.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【表３】 [Table 3]
【００２４】次ぎに、各試験片の特性評価を行うため
に、それぞれの硬さを測定するとともに、腐食試験およ
び摩耗試験を行った。腐食試験は、室温で、５％弗化水
素酸に３０時間浸漬し、腐食減量を測定して耐食性を評
価した。また、摩耗試験は、金属同士の凝着摩耗をシミ
ュレートするため、大越式迅速摩耗試験機を用い、相手
材にＳＫＤ１１相当材（ＨＲＣ６１）を使用し、最終荷
重１８．９ｋｇｆ、摩擦速度２．３７ｍ／Ｓ、摩擦距離
２００ｍ、室温、無潤滑の条件下で試験を行い、摩耗量
を測定して耐摩耗性を評価した。さらに、樹脂中の硬質
添加剤による摩耗をシミュレートするためにアブレシブ
摩耗試験を行った。具体的には、相手材に３２０番のＳ
ｉＣ研磨紙を用いて荷重２ｋｇｆ、速度３．６ｍ／ｓ
（６０往復／分）で試験を行った。なお摩耗量は、４０
０回毎の摩耗減量の平均値とした。Next, in order to evaluate the characteristics of each test piece, its hardness was measured, and a corrosion test and a wear test were performed. In the corrosion test, the corrosion resistance was evaluated by immersing in 5% hydrofluoric acid for 30 hours at room temperature and measuring the corrosion weight loss. Further, in the wear test, in order to simulate adhesion wear between metals, an Ogoshi-type rapid wear tester was used, SKD11 equivalent material (HRC61) was used as the mating material, and final load was 18.9 kgf and friction speed was 2. The test was performed under the conditions of 37 m / S, friction distance of 200 m, room temperature, and no lubrication, and the wear amount was measured to evaluate the wear resistance. In addition, an abrasive wear test was conducted to simulate wear due to hard additives in the resin. Specifically, the mating material is the 320th S
Using iC polishing paper, load 2kgf, speed 3.6m / s
The test was performed at (60 reciprocations / minute). The wear amount is 40
The average value of wear reduction every 0 times was used.
【００２５】これらの試験結果を表４に示す。その結
果、比較例１（Ｎｉ基耐食合金）は耐食性には優れてい
るものの耐摩耗性に劣っており、例えば、樹脂にガラス
繊維などを添加した複合材料の成形に対しては好適な材
料ではない。また、比較例２（Ｎｉ基自溶性合金）は、
耐摩耗性は十分とはいえないものの、ある程度の特性は
確保されている。しかし、耐食性の点では明らかに劣っ
ている。The results of these tests are shown in Table 4. As a result, Comparative Example 1 (Ni-based corrosion resistant alloy) is excellent in corrosion resistance but inferior in wear resistance. For example, it is not a suitable material for molding a composite material in which glass fiber or the like is added to resin. Absent. Comparative Example 2 (Ni-based self-fluxing alloy)
Although it cannot be said that the wear resistance is sufficient, a certain degree of characteristics are secured. However, it is clearly inferior in terms of corrosion resistance.
【００２６】これに対し、実施例１〜１０の試験片は、
ＷＣ、ＴｉＣ等の炭化物によって耐アブレシブ摩耗性が
向上しており、例えば、樹脂中の硬質添加剤による摩耗
を防止する。また、複合ほう化物が潤滑剤としての効力
を発揮しており、大越式摩耗試験では、自身（固定試験
片）および相手材（回転試験片）のいずれの摩耗量も小
さく、構成部材の金属同士の接触により生じる摩耗にお
いて、相手材に対する攻撃性をやわらげ、かつ金属同士
の凝着摩耗をやわらげている。さらに、腐食試験におけ
る腐食量も少なく、例えば、樹脂中から発生するガスに
よる高腐食環境下でも、高ＣｒのＮｉマトリックスと複
合ほう化物が高い耐食性を示す。以上のように、本発明
の複合材料は、比較材と異なり、耐摩耗性および耐食性
のいずれにおいても優れた結果が得られた。なお、表中
で回転試験片の摩耗量が負の値を示しているものは、凝
着により固定試験片の材料が回転試験片に付着したため
である。On the other hand, the test pieces of Examples 1 to 10 were
The abrasive wear resistance is improved by carbides such as WC and TiC, and for example, wear due to the hard additive in the resin is prevented. In addition, the compound boride is effective as a lubricant. In the Ogoshi-type wear test, both the self (fixed test piece) and the mating material (rotating test piece) wear little, and With respect to the wear caused by the contact between the materials, the aggressiveness to the mating material is softened, and the adhesive wear between the metals is softened. Further, the amount of corrosion in the corrosion test is small, and for example, even in a highly corrosive environment due to the gas generated from the resin, the high Cr Ni matrix and the complex boride exhibit high corrosion resistance. As described above, the composite material of the present invention, unlike the comparative material, was excellent in both wear resistance and corrosion resistance. In the table, the amount of wear of the rotating test piece shows a negative value because the material of the fixed test piece adheres to the rotating test piece due to adhesion.
【００２７】[0027]
【表４】 [Table 4]
【００２８】[0028]
【発明の効果】以上説明したように、本願発明の複合材
料によれば、ほう化物と炭化物を主体とする硬質相をＮ
ｉ基合金で結合したので、高耐食性だけでなく、耐凝
着、耐アブレシブ摩耗の両特性を具備する耐摩耗材料と
して優れた特性が得られる効果がある。したがって、過
酷な成形条件下で使用される樹脂加工機械用のシリン
ダ、スクリュ、摩擦リング、逆流防止リングなどの構成
摺動材料として最適な複合材料が得られる効果がある。As described above, according to the composite material of the present invention, the hard phase mainly composed of boride and carbide is N
Since the i-based alloy is used for bonding, not only high corrosion resistance but also excellent properties as a wear resistant material having both properties of adhesion resistance and abrasive wear resistance are obtained. Therefore, there is an effect that the optimum composite material can be obtained as a constituent sliding material such as a cylinder, a screw, a friction ring, a backflow prevention ring for a resin processing machine used under severe molding conditions.
【図１】図１は実施例焼結体の一つの金属組織写真（倍
率２０００倍）である。FIG. 1 is a photograph of a metal structure of a sintered body of Example (magnification: 2000 times).
Claims (3)
う化物を主体とする硬質層が分散した複合材料であっ
て、前記マトリックスおよび硬質層は、総量でＢ：２〜
６重量％、Ｃｒ：２１〜３８重量％、Ｍｏ：８〜２２重
量％、Ｗ：０．５〜１２重量％、Ｆｅ：３〜６重量％、
Ｃ：０．４〜３重量％、Ｃｕ：０〜２重量％を含有し、
さらに、Ｔｉ：２〜２０重量％、Ｔａ：１〜５重量％の
１種または２種を含有し、残部がＮｉ及び不可避的不純
物よりなることを特徴とする高耐食耐摩耗性複合材料1. A composite material in which a hard layer mainly containing carbide and boride is dispersed in a Ni-based matrix, and the total amount of the matrix and the hard layer is B: 2 to 2.
6% by weight, Cr: 21 to 38% by weight, Mo: 8 to 22% by weight, W: 0.5 to 12% by weight, Fe: 3 to 6% by weight,
C: 0.4 to 3% by weight, Cu: 0 to 2% by weight,
Further, a high corrosion-resistant and abrasion-resistant composite material containing Ti: 2 to 20% by weight, Ta: 1 to 5% by weight, one or two kinds, and the balance being Ni and inevitable impurities.
物および窒化物を主体とする硬質層が分散した複合材料
であって、前記マトリックスおよび硬質層は、総量で
Ｂ：２〜６重量％、Ｃｒ：２１〜３８重量％、Ｍｏ：８
〜２２重量％、Ｗ：０．５〜１２重量％、Ｆｅ：３〜６
重量％、Ｃ：０．４〜３重量％、Ｎ：３重量％以下、Ｃ
ｕ：０〜２重量％を含有し、さらに、Ｔｉ：２〜２０重
量％、Ｔａ：１〜５重量％の１種または２種を含有し、
残部がＮｉ及び不可避的不純物よりなることを特徴とす
る高耐食耐摩耗性複合材料2. A composite material in which a hard layer containing carbide, boride and nitride as main components is dispersed in a Ni-based matrix, and the matrix and the hard layer have a total amount of B: 2 to 6% by weight and Cr. : 21 to 38% by weight, Mo: 8
-22% by weight, W: 0.5-12% by weight, Fe: 3-6
% By weight, C: 0.4 to 3% by weight, N: 3% by weight or less, C
u: 0 to 2% by weight, further, Ti: 2 to 20% by weight, Ta: 1 to 5% by weight of 1 type or 2 types,
High corrosion resistance and wear resistance composite material characterized by the balance being Ni and inevitable impurities
が６〜２５％であることを特徴とする請求項１または２
に記載の高耐食耐摩耗性複合材料3. The hard layer according to claim 1, wherein the total content of W, Ti and Ta is 6 to 25%.
High corrosion resistance and wear resistance composite material described in
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30269494A JP3487935B2 (en) | 1994-11-14 | 1994-11-14 | High corrosion and wear resistant composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30269494A JP3487935B2 (en) | 1994-11-14 | 1994-11-14 | High corrosion and wear resistant composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08134570A true JPH08134570A (en) | 1996-05-28 |
| JP3487935B2 JP3487935B2 (en) | 2004-01-19 |
Family
ID=17912074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30269494A Expired - Fee Related JP3487935B2 (en) | 1994-11-14 | 1994-11-14 | High corrosion and wear resistant composite material |
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| Country | Link |
|---|---|
| JP (1) | JP3487935B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6367748B1 (en) | 2000-02-12 | 2002-04-09 | Solvisions Technologies Int'l | Apparatus for providing desktop mobility for desktop electronic devices |
| WO2020086971A1 (en) * | 2018-10-26 | 2020-04-30 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
| WO2021045183A1 (en) | 2019-09-06 | 2021-03-11 | 日立金属株式会社 | Ni-BASED ALLOY, Ni-BASED ALLOY POWDER, NI-BASED ALLOY MEMBER, AND PRODUCT PROVIDED WITH Ni-BASED ALLOY MEMBER |
-
1994
- 1994-11-14 JP JP30269494A patent/JP3487935B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6367748B1 (en) | 2000-02-12 | 2002-04-09 | Solvisions Technologies Int'l | Apparatus for providing desktop mobility for desktop electronic devices |
| WO2020086971A1 (en) * | 2018-10-26 | 2020-04-30 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
| CN113195759A (en) * | 2018-10-26 | 2021-07-30 | 欧瑞康美科（美国）公司 | Corrosion and wear resistant nickel base alloy |
| CN113195759B (en) * | 2018-10-26 | 2023-09-19 | 欧瑞康美科（美国）公司 | Corrosion and wear resistant nickel base alloy |
| US11939646B2 (en) | 2018-10-26 | 2024-03-26 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
| WO2021045183A1 (en) | 2019-09-06 | 2021-03-11 | 日立金属株式会社 | Ni-BASED ALLOY, Ni-BASED ALLOY POWDER, NI-BASED ALLOY MEMBER, AND PRODUCT PROVIDED WITH Ni-BASED ALLOY MEMBER |
| US11821059B2 (en) | 2019-09-06 | 2023-11-21 | Proterial, Ltd. | Ni-based alloy, Ni-based alloy powder, Ni-based alloy member, and product including Ni-based alloy member |
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| JP3487935B2 (en) | 2004-01-19 |
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