JPH0456745A - Double boride hard alloy source - Google Patents
Double boride hard alloy sourceInfo
- Publication number
- JPH0456745A JPH0456745A JP16401890A JP16401890A JPH0456745A JP H0456745 A JPH0456745 A JP H0456745A JP 16401890 A JP16401890 A JP 16401890A JP 16401890 A JP16401890 A JP 16401890A JP H0456745 A JPH0456745 A JP H0456745A
- Authority
- JP
- Japan
- Prior art keywords
- boride
- hard alloy
- source
- complex boride
- type
- 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
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 61
- 239000000956 alloy Substances 0.000 title claims abstract description 61
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract 3
- 229910052758 niobium Inorganic materials 0.000 claims description 14
- 229910052735 hafnium Inorganic materials 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000010409 thin film Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 238000005240 physical vapour deposition Methods 0.000 abstract description 8
- 239000010408 film Substances 0.000 abstract description 7
- 229910052796 boron Inorganic materials 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000011368 organic material Substances 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 2
- 238000004544 sputter deposition Methods 0.000 abstract description 2
- 238000007740 vapor deposition Methods 0.000 abstract 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 238000007733 ion plating Methods 0.000 abstract 1
- 239000013077 target material Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 238000005245 sintering Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910000521 B alloy Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 241001024304 Mino Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- -1 carbon Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910020674 Co—B Inorganic materials 0.000 description 1
- 229910016285 MxNy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、蒸着法、イオンブレーティング法およびスッ
パタリング法などのＰ Ｖ Ｄ （ＰｈｙｓｉｃａｌＶ
ａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）法により、硼素およ
び２種類以上の金属元素を含む耐摩耗性および耐食性に
優れたコーティング薄膜を形成するのに用いる複硼化物
系硬質合金ソース（蒸着源およびターゲット）に関する
。Detailed Description of the Invention [Industrial Application Field] The present invention is applicable to P V D (Physical V
The present invention relates to a complex boride-based hard alloy source (evaporation source and target) used to form a thin coating film containing boron and two or more metal elements with excellent wear resistance and corrosion resistance by apor deposition method.
［従来の技術］
機械部品、切削工具、有機材料などに、耐摩耗性、耐食
性、耐熱性などを付与する目的で、高硬度を有するＴｉ
Ｃなとの炭化物、Ａ １２０３などの酸化物、ＴｉＮな
との窒化物の薄膜を蒸着法、イオンブレーティング法お
よびスッパタリング法などのＰＶＤ法、およびＣＶＤ
（Ｃｈｅｍｉｃａｌ ＶａｐｏｒＤｅｐｏｓｉｔｉｏｎ
）法などにより形成し、表面保護皮膜として用いること
は良く知られている。[Prior art] Ti, which has high hardness, is used to impart wear resistance, corrosion resistance, heat resistance, etc. to mechanical parts, cutting tools, organic materials, etc.
Thin films of carbides such as carbon, oxides such as A 1203, and nitrides such as TiN can be deposited using PVD methods such as evaporation methods, ion blasting methods and sputtering methods, and CVD methods.
(Chemical Vapor Deposition
) method and use as a surface protective film is well known.
高硬度の耐摩耗性、耐食性、耐熱性を有する物質として
は、炭化物、酸化物、窒化物のほかに硼化物が存在する
。硼化物は、炭化物などに比較して難焼結性であるため
、硼化物のコーティングは、もっばら固体のソースを必
要としないＣＶＤ法により行われているのが現状である
。わずかにポットプレス法により作成した焼結体を用い
たＰＶＤ法によるコーティングが試みられているが、こ
れもＴ ｉ Ｂ２、ＺｒＢ２などの２元硼化物に限られ
、組成的自由度は限られている。In addition to carbides, oxides, and nitrides, borides are examples of substances that have high hardness, wear resistance, corrosion resistance, and heat resistance. Since borides are more difficult to sinter than carbides and the like, boride coatings are currently mostly carried out by the CVD method, which does not require a solid source. A few attempts have been made to coat a sintered body made by the pot press method using the PVD method, but this is also limited to binary borides such as T i B2 and ZrB2, and the degree of compositional freedom is limited. There is.
［発明が解決しようとする課題］
ＣＶＤ法により硼化物のコーティング薄膜を形成する場
合、基板温度は通常７５０℃以上の高温が必要なため、
基板の変質を招いたり、耐熱性の乏しい材料、特に有機
材料へのコーティングができないという問題があり、Ｐ
ＶＤ法により低温基板上にコーティング薄膜の形成が可
能な、固体の硼化物系ソースが望まれている。[Problems to be Solved by the Invention] When forming a boride coating thin film by the CVD method, the substrate temperature usually needs to be at a high temperature of 750°C or higher.
There are problems with the deterioration of the substrate and the inability to coat materials with poor heat resistance, especially organic materials.
What is desired is a solid boride-based source that allows the formation of thin coatings on low-temperature substrates using the VD method.
近年、耐摩耗性、耐食性を有する複硼化物系硬質材料の
一つとしてＭｏ２ＦｅＢ２、Ｍ ０２Ｎ Ｉ Ｂ ２な
どの複硼化物を硬質相とし、これをＦｅ、Ｎｉなどの遷
移金属により結合した硬質合金が提案されているが（特
公昭６０−５７４９９、特開昭６２−１９６３５３）、
これらを利用した複硼化物系硬質合金ソース（蒸着源お
よびターゲット）は存在しないため、ＰＶＤ法ばかりで
なくＣＶＤ法によっても、このような複硼化物系硬質合
金ソースを用いたボロンを含むコーティング薄膜を形成
できないという問題点があった。In recent years, hard alloys in which complex borides such as Mo2FeB2 and M 02N I B 2 are used as a hard phase and bonded with transition metals such as Fe and Ni have been developed as one of complex boride-based hard materials that have wear resistance and corrosion resistance. has been proposed (Japanese Patent Publication No. 60-57499, Japanese Patent Publication No. 62-196353),
Since there are no complex boride-based hard alloy sources (evaporation sources and targets) that utilize these, boron-containing coating thin films using such complex boride-based hard alloy sources can be produced not only by PVD but also by CVD. There was a problem that it could not be formed.
本発明は、主としてＰＶＤ法により耐摩耗性および耐食
性に優れたコーティング薄膜を形成するのに用いる、Ｍ
ｘＮｙＢ型複硼化物系の硬質相を含み、組成的自由度を
有する、固体の複硼化物系硬質合金ソースを提供するこ
と目的としている。The present invention mainly focuses on M
The object of the present invention is to provide a solid complex boride hard alloy source that includes an xNyB type complex boride hard phase and has a degree of compositional freedom.
［課題を解決するための手段］ 上記目的を達成するためには、Ｆｅ、Ｃｒ。[Means to solve the problem] In order to achieve the above purpose, Fe, Cr.
Ｃｏ、Ｎｉの中から選ばれた１種以上の元素または合金
よりなるマトリックス中に、ＭｘＮｙＢ型（以下Ｍ、
Ｎは金属、ｘ、ｙはＭ、 Ｎが化合物を形成するに
必要な化学量論的な数値を表す）複硼化物を４０〜９９
％含む複硼化物系硬質合金ソース（蒸着源およびターゲ
ット）であって、該複硼化物において、ＭはＭｏおよび
／またはＷ、 ＮはＦｅ、Ｃｒ、Ｃｏ、Ｎｉの中から
選ばれた１種以上の元素よりなり、該ソースに対してＢ
含有量が２〜８％、Ｍｏおよび／またはＷ含有量が、（
Ｍｏおよび／またはＷ）／Ｂのモル比で０．５０〜１．
５０を満足する範囲内にあり、残部がＦｅ。MxNyB type (hereinafter M,
N is a metal;
%, in which M is Mo and/or W, and N is one selected from Fe, Cr, Co, and Ni. It consists of the above elements, and B
The content is 2-8%, the Mo and/or W content is (
Mo and/or W)/B molar ratio of 0.50 to 1.
50, and the remainder is Fe.
Ｃｒ、Ｃｏ、Ｎｉの中から選ばれた１種以上の元素また
は合金および不可避的不純物よりなることを特徴とする
複硼化物系硬質合金ソース（以下本硬質合金ソースと呼
ぶ）を用いることが効果的である。It is effective to use a complex boride-based hard alloy source (hereinafter referred to as the main hard alloy source) characterized by consisting of one or more elements or alloys selected from Cr, Co, and Ni and unavoidable impurities. It is true.
さらに耐摩耗性および耐食性を向上させるためには、４
０〜９９％のＭｘＮｙＢ型（ＭはＭｏおよび／またはＷ
とＴｉ、Ｖ、Ｎｂ、Ｔａ、Ｈｆ。In order to further improve wear resistance and corrosion resistance, 4
0-99% MxNyB type (M is Mo and/or W
and Ti, V, Nb, Ta, Hf.
Ｚｒの中から選ばれた１種以上の元素、ＮはＦｅ。One or more elements selected from Zr, N is Fe.
Ｃｒ、Ｃｏ、Ｎｉの中から選ばれた１種以上の元素）複
硼化物を、Ｆｅ、Ｃｒ、Ｃｏ、Ｎｉの中から選ばれた１
種以上の元素と、Ｍｏ、 Ｗ、 Ｃｕ。(one or more elements selected from among Cr, Co, and Ni) complex boride, one or more elements selected from among Fe, Cr, Co, and Ni
Elements more than species, Mo, W, Cu.
Ｔｉ、Ｖ、Ｎｂ、Ｔａ、Ｈｆ、Ｚｒ、Ｓｉの中か９選ば
れた１種以上の元素との合金よりなるマトリックスによ
り結合した硬質合金ソースであり、かつ合金中のＣｕ、
Ｔｉ、 Ｖ、 Ｎｂ、 Ｔａ、 Ｈｆ。A hard alloy source bonded by a matrix consisting of an alloy with one or more elements selected from among Ti, V, Nb, Ta, Hf, Zr, and Si, and Cu in the alloy,
Ti, V, Nb, Ta, Hf.
Ｚｒ、Ｓｉの中から選ばれた１種以上の元素の含有量の
合計が０．５〜２５％である複硼化物系硬質合金ソース
を用いると一層効果的である。It is more effective to use a complex boride hard alloy source in which the total content of one or more elements selected from Zr and Si is 0.5 to 25%.
以下本発明の限定理由について詳細に説明する。The reasons for the limitations of the present invention will be explained in detail below.
本硬質合金ソースの硬質相を構成するＭｘＮｙＢ型複硼
化物において、ＭをＭｏおよび／またはＷ、ＮをＦｅ、
Ｃｒ、Ｃｏ、Ｎｉの中から選ばれた１種以上の元素と限
定したのは、（Ｍｏ、Ｗ）（Ｆｅ、Ｃｒ、Ｃｏ、Ｎｉ）
−Ｂ系状態図において、高硬度を有するＭｏ２ＦｅＢ
２、Ｍｏ２ＮｊＢ２、Ｗ２Ｎ１Ｂ２、Ｗ２Ｎ１Ｂ２、Ｍ
ｏ２ＣｏＢ２、Ｗ２ＣｏＢ２、ＷＦｅＢ、ＭｏＣｏＢ、
ＭｏＣｒＢなどのｒ’Ｌ Ｎ ｏ、 ｓＢ 、（Ｍ２Ｎ
Ｂ ２）およびＭＮＢ型複型化硼化物在し、これらの
複硼化物中には、Ｍｏ２ＮｉＢ２、Ｗ２Ｎ１Ｂ２、Ｗ２
ＣｏＢ２など同じ結晶構造を有するものが多く、相互に
固溶しあうと共に、これらの複硼化物をＦｅ、 Ｃｒ
、 Ｃｏ。In the MxNyB type complex boride constituting the hard phase of the present hard alloy source, M is Mo and/or W, N is Fe,
One or more elements selected from Cr, Co, and Ni are limited to (Mo, W) (Fe, Cr, Co, Ni)
-Mo2FeB with high hardness in the B system phase diagram
2, Mo2NjB2, W2N1B2, W2N1B2, M
o2CoB2, W2CoB2, WFeB, MoCoB,
r'L No, sB, (M2N
B2) and MNB type complex borides, and these complex borides include Mo2NiB2, W2N1B2, W2
Many of them have the same crystal structure, such as CoB2, and they are mutually dissolved, and these complex borides are combined with Fe, Cr.
, Co.
Ｎｉ、の中から選ばれた１種以上の元素または合金より
なる結合相により結合した硬質合金ソースは、優れた耐
摩耗性、耐食性と組成的自由度を有するコーティング薄
膜を、ＰＶＤ法により形成し得るためである。上記Ｍ１
Ｎｏ５Ｂ、およびＭＮＢ型で表される複硼化物は、非化
学量論的化合物であり、ある組成の幅を持つ複硼化物で
あることが知られている。よって（Ｍｏ＋ Ｗ）
（Ｆ ｅ。A hard alloy source bonded by a binder phase consisting of one or more elements or alloys selected from Ni, can be used to form a coating thin film with excellent wear resistance, corrosion resistance, and compositional freedom by the PVD method. It's to get it. M1 above
It is known that complex borides represented by No5B and MNB types are non-stoichiometric compounds and have a certain range of compositions. Therefore (Mo+W)
(Fe.
Ｃｒ、Ｃｏ、Ｎｉ） −Ｂ系状態図中に存在する、組成
範囲を有するＭＩＮｏ、５８１および ＭＮＢ型複型化
硼化物よびこれら複硼化物の相互に固溶し合ったものを
総称して以下ＭｘＮｙＢ型複硼化型上硼化物とにする。MINo, 581, and MNB type complex borides having a composition range existing in the Cr, Co, Ni) -B system phase diagram and mutual solid solutions of these complex borides are collectively referred to as follows: MxNyB type complex boride superboride.
ここでＸおよびｙは、ある組成範囲を有するＭＩＮｏ、
５８１およびＭＮＢ型複型化硼化物成する必要から、そ
れぞれ０．５≦Ｘ≦１．５．０．２５≦ｙ≦１．５、好
ましくは０．６≦Ｘ≦１．４．０．３≦ｙ≦１．４とす
る。Here, X and y are MINo having a certain composition range,
581 and MNB type complex boride, 0.5≦X≦1.5.0.25≦y≦1.5, preferably 0.6≦X≦1.4.0.3, respectively. ≦y≦1.4.
本硬質合金ソースを用いて形成したコーティング薄膜に
、最低限の耐摩耗性を付与するためには、ＭｘＮｙＢ型
複硼化物の量は、最低４０％必要である。一方コーティ
ング薄膜の耐摩耗性を高めるためには、ＭｘＮｙＢ型複
硼化物の量はできるだけ多い方が好ましいが、９９％を
越えると本硬質合金ソース自体が脆くなり取扱いが困難
になる。つまり本硬質合金ソースに、取扱い上支障のな
い強度をもたせるためには、少なくとも１％の結合相が
必要である。よって本硬質合金ソース中に占めるＭｘＮ
ｙＢ型複硼化物の量は４０〜９９％、好ましくは５０〜
９８％とする。In order to impart a minimum wear resistance to the coating thin film formed using the present hard alloy source, the amount of MxNyB type complex boride is required to be at least 40%. On the other hand, in order to improve the wear resistance of the coating thin film, it is preferable that the amount of MxNyB type complex boride be as large as possible, but if it exceeds 99%, the hard alloy source itself becomes brittle and difficult to handle. In other words, at least 1% of the binder phase is required in order to provide the present hard alloy source with strength that does not pose a problem in handling. Therefore, MxN in the present hard alloy source
The amount of yB type complex boride is 40 to 99%, preferably 50 to 99%.
It shall be 98%.
上記（Ｍｏ、 Ｗ） −（Ｆ ｅ、 Ｃｒ、 Ｃｏ、
Ｎ １）−Ｂ系状態図中には、ＭｘＮｙＢ型複硼化
物の他にＭｏＢ、ＷＢ、Ｆｅ２Ｂ、ＦｅＢ、Ｃｒ２Ｂな
ど多くのＭ’ｚＢ型（Ｍ’はＦｅ、Ｃｒ、Ｃｏ、Ｎｉ。The above (Mo, W) - (Fe, Cr, Co,
In the N1)-B system phase diagram, in addition to the MxNyB type complex boride, there are many M'zB types such as MoB, WB, Fe2B, FeB, and Cr2B (M' is Fe, Cr, Co, and Ni.
Ｍｏ、Ｗの中から選ばれた１種類の元素、２はＭ′が化
合物を形成するに必要な化学量論的な数値を表す）２元
硼化物が存在する。ＰＶＤ法により形成されたコーティ
ング薄膜は、薄膜形成時に急冷されるため非晶質あるい
は過飽和固溶体を形成することがしばしば認められる。There is a binary boride of one type of element selected from Mo and W (2 represents the stoichiometric value necessary for M' to form a compound). It is often observed that coating thin films formed by the PVD method form an amorphous or supersaturated solid solution because they are rapidly cooled during thin film formation.
さらにＢは軽元素であるため、他の金属元素に比較して
薄膜形成時の歩留は悪い。よってＢは、ＭｘＮｙＢ型複
硼化物形成に必要な量よりも過剰に添加する必要がある
場合がある。この場合、本硬質合金ソース中の硼化物相
としては、ＭｘＮｙＢ型複硼化物の他にＭ’ｚＢ型硼化
型炉化物されるが、Ｍ’ｚＢ型硼化型炉化物ＭｘＮｙＢ
型複硼化物の置換量が５０％未満てあれば、最終的なコ
ーティング薄膜の特性に与える影響は少ない。よって、
本硬質合金ソース中におけるＭ’ｚＢ型硼化型炉化物Ｍ
ｘＮｙＢ型複硼化物の置換量は５０％未満とする。なお
本硬質合金ソース中にさらにＴｉ、 Ｖ、 Ｎｂ、
Ｔａ、 Ｈｆ。Furthermore, since B is a light element, the yield during thin film formation is lower than that of other metal elements. Therefore, B may need to be added in excess of the amount required to form the MxNyB type complex boride. In this case, the boride phase in the present hard alloy source includes an M'zB type boride furnace in addition to the MxNyB type complex boride;
If the amount of type complex boride substitution is less than 50%, it will have little effect on the properties of the final coating film. Therefore,
M'zB type borided furnace compound M in this hard alloy source
The amount of substitution of the xNyB type complex boride is less than 50%. In addition, this hard alloy source further contains Ti, V, Nb,
Ta, Hf.
Ｚｒが添加された場合は、Ｍ′がこれらの元素となった
Ｍ’ｚＢ型硼化型炉化物される場合もある。When Zr is added, an M'zB type boride-type furnace compound in which M' is one of these elements may be obtained.
硼化物形成元素であるＢは、本硬質合金ソース中に複硼
化物を最低４０％形成させるために２％、最大９９％形
成させるためには８％必要である。B, which is a boride-forming element, is required to be 2% to form a complex boride of at least 40% in the present hard alloy source, and 8% to form a maximum of 99%.
よって本硬質合金ソース中のＢ含有量は、２〜８％とす
る。Therefore, the B content in the present hard alloy source is set to 2 to 8%.
ＭｏおよびＷは、Ｂ同様ＭｘＮｙＢ型複硼化物を形成す
る主要な元素であり、（Ｍｏおよび／またはＷ）／Ｂの
モル比で０．５０〜１．５０を満足する範囲内にある時
、ＭｘＮｙＢ型複硼化物を主体とする硼化物が形成され
る。よってＭｏおよび／またはＷ含有量は、（Ｍｏおよ
び／またはＷ）／Ｂのモル比で０．５０〜】、５ｏ、好
ましくは０．６〜１．４を満足する範囲内とする。Mo and W, like B, are the main elements forming the MxNyB type complex boride, and when the molar ratio of (Mo and/or W)/B is within the range of 0.50 to 1.50, A boride mainly consisting of MxNyB type complex boride is formed. Therefore, the Mo and/or W content is within a range that satisfies the molar ratio of (Mo and/or W)/B from 0.50 to 5o, preferably from 0.6 to 1.4.
周期律表のＩＶａ族のＴｉ、Ｚｒ、ＨｆおよびＶａ族の
Ｖ、Ｎｂ、Ｔａの各元素は、ＭｘＮｙＢ型複硼化型中硼
化物中よび／またはＷの一部と置換し、ＭｘＮｙＢ型複
硼化物の硬度上昇に寄与するとともに、一部はマトリク
ラス中にも固溶し、コーティング薄膜の耐摩耗性向上に
つながる。上記効果は、これらの元素の０．５％添加か
ら認められるが、２５％以上添加しても添加量はどの効
果は認められなくなる。またこれらの元素は、単独添加
したときばかりでなく、複合添加した場合も同様の効果
を示す。よってＴｉ、 Ｚｒ、 Ｈｆ、 Ｖ。Each element of Ti, Zr, Hf in group IVa of the periodic table and V, Nb, Ta in group Va is substituted with a part of W in the MxNyB type complex boride and/or a part of W. In addition to contributing to an increase in the hardness of the boride, some of it also dissolves in the matrix, leading to improved wear resistance of the coating thin film. The above effects can be observed from the addition of 0.5% of these elements, but even if 25% or more of these elements are added, no effect can be observed. Furthermore, these elements exhibit similar effects not only when added singly but also when added in combination. Therefore, Ti, Zr, Hf, V.
Ｎｂ、Ｔａの添加量は、これらの元素の合計で０．５〜
２５％とする。The amount of Nb and Ta added is 0.5 to 0.5 in total of these elements.
It shall be 25%.
ＳｉおよびＣｕは、本硬質合金ソースのマトリクラス中
に固溶し、各々、コーティング薄膜の耐酸化性および耐
食性の向上に寄与する。ＳｉおよびＣｕの添加量は、０
．５％未満では上記効果は認められず、２５％を越えて
添加すると耐酸化性および耐食性は向上するものの、コ
ーティング薄膜の脆化を招く。ＳｉおよびＣｕは、Ｔｉ
、Ｚｒ。Si and Cu form a solid solution in the matrix class of the present hard alloy source, and each contribute to improving the oxidation resistance and corrosion resistance of the coating thin film. The amount of Si and Cu added is 0.
．． If it is less than 5%, the above effect will not be observed, and if it is added in excess of 25%, the oxidation resistance and corrosion resistance will improve, but the coating thin film will become brittle. Si and Cu are Ti
, Zr.
Ｈｆ、Ｖ、Ｎｂ、Ｔａと複合添加しても上記効果を有す
る。よってＳｉおよびＣｕの添加量は、Ｔｉ、 Ｚｒ
、 Ｈｆ、 Ｖ、 Ｎｂ、 Ｔａｓ Ｓｉ、
Ｃｕの合計として０．５〜２５％とする。Even when added in combination with Hf, V, Nb, and Ta, the above effects can be obtained. Therefore, the amounts of Si and Cu added are as follows: Ti, Zr
, Hf, V, Nb, Tas Si,
The total amount of Cu is 0.5 to 25%.
本硬質合金ソース中に含まれる不可避的不純物元素の主
なものは、ＡＩ、 Ｍｎ、 Ｍｇ、 Ｐ、 Ｓ。The main unavoidable impurity elements contained in this hard alloy source are AI, Mn, Mg, P, and S.
Ｎ、 Ｏ，Ｃであり、これら不純物元素の含有量は極力
少ないことにこしたことはないが、これら不純物元素の
合計が２％以下であれば、最終的なコーティング薄膜の
特性に与える影響は少ない。よって本硬質合金ソース中
に含まれる不可避的不純物元素の含有量は、複数の不純
物元素の合計で２％以下とする。N, O, and C, and it is best to keep the content of these impurity elements as low as possible, but if the total content of these impurity elements is less than 2%, the effect on the properties of the final coating thin film will be minimal. few. Therefore, the content of unavoidable impurity elements contained in the present hard alloy source is set to 2% or less in total of a plurality of impurity elements.
以下本硬質合金ソースの製造方法について述べる。The method for manufacturing the present hard alloy source will be described below.
本硬質合金ソースは、特公昭６０−５７４９９あるいは
特開昭６２−１９６３５３に開示されているように、ボ
ロン源として、Ｆｅ−ＢまたはＦｅ−Ｂ系合金粉末、Ｎ
１−ＢまたはＮ１−Ｂ系合金粉末、Ｃｏ−ＢまたはＣｏ
−Ｂ系合金粉末、フェロボロン粉末、ニッケルボロン粉
末、Ｆｅ。This hard alloy source uses Fe-B or Fe-B alloy powder, N
1-B or N1-B alloy powder, Co-B or Co
-B alloy powder, ferroboron powder, nickel boron powder, Fe.
Ｃｒ、 Ｃｏ、 Ｎｉ、 Ｍｏ、 Ｗ、 Ｔ ｉ
、 Ｖ、 Ｎｂ。Cr, Co, Ni, Mo, W, Ti
, V, Nb.
Ｔａ、Ｈｆ、Ｚｒの各硼化物粉末、もしくはＢ単体粉末
を用い、これらの粉末とＦｅ、 Ｃｒ、 Ｃｏ。Boride powders of Ta, Hf, and Zr, or single B powders are used, and these powders are combined with Fe, Cr, and Co.
Ｎｉ、 Ｍｏ、 Ｗ、 Ｔｉ、 Ｖ、 Ｎｂ、
Ｔ’ａ、 Ｈｆ。Ni, Mo, W, Ti, V, Nb,
T'a, Hf.
Ｚｒ、Ｓｉ、Ｃｕの単体金属粉末、もしくはこれらの元
素を２種類以上含む合金粉末とを所定の組成になるよう
に配合し、必要に応じて粉末表面の酸化皮膜還元のため
に少量の炭素粉もしくは炭化物を添加し、これらの混合
粉末を、例えば振動ボールミルを用いて、有機溶媒中で
湿式混合粉砕後、乾燥・造粒・成形を行い、該成形体を
非酸化性雰囲気中で反応焼結を行い、焼結中にＭｘＮｙ
Ｂ型複硼化物を形成させることにより製造される。反応
焼結は通常、９００〜１５００’Ｃで１〜１２０分間行
う。焼結雰囲気としては、粉末の酸化防止のため、真空
、還元ガスあるいは不活性カスなどの非酸化性雰囲気を
用いることが重要である。Single metal powders of Zr, Si, and Cu or alloy powders containing two or more of these elements are blended to a predetermined composition, and if necessary, a small amount of carbon powder is added to reduce the oxide film on the powder surface. Alternatively, carbide is added, and the mixed powder is wet mixed and pulverized in an organic solvent using, for example, a vibrating ball mill, followed by drying, granulation, and molding, and the molded body is subjected to reaction sintering in a non-oxidizing atmosphere. and MxNy during sintering.
It is manufactured by forming a B-type complex boride. Reactive sintering is typically performed at 900-1500'C for 1-120 minutes. As the sintering atmosphere, it is important to use a non-oxidizing atmosphere such as vacuum, reducing gas, or inert scum to prevent oxidation of the powder.
本硬質合金ソースの焼結後の密度は、均一なコーティン
グ薄膜を得るためにはできるだけ高いことが好ましいが
、真密度の５５％以上の密度を有すれば、実用的には取
扱いに支障のない強度を有する。The density of this hard alloy source after sintering is preferably as high as possible in order to obtain a uniform coating thin film, but if the density is 55% or more of the true density, there will be no practical problem in handling. Has strength.
本硬質合金ソースの製造方法として一般的な焼結法につ
いて述べたが、該目的を達成するためには、熱間静水圧
プレス法、ホットプレス法、通電焼結法など焼結中にＭ
ｘＮｙＢ型複硼化物の形成反応が生じる焼結法であれば
いずれの焼結法でも差し支えない。We have described the general sintering method as a manufacturing method for this hard alloy source, but in order to achieve this purpose, M
Any sintering method may be used as long as it causes a reaction to form an xNyB type complex boride.
［実施例］
実施例 Ｉ
Ｆ ｅ −１０，９Ｂ −１４，３Ｃｒ合金粉： １８
．１％、ＭｏＢ粉＝４０％、純Ｍｏ粉：９．２％、カー
ボニルＮｉ粉：８．４％、純Ｃｒ粉：１Ｂ、７％、カー
ボニルＦｅ粉：５．４％、グラファイト粉：０．２％を
配合し、振動ボールミルによりアセトン中で２８時時間
式混合粉砕し、乾燥・造粒・成形後、真空中１２７５℃
で２０分間焼結し、はぼ真密度の合金組成がＦ ｅ−６
Ｂ−４５Ｍｏ−２１，３Ｃｒ−８，４Ｎｉの、Ｍｏ２Ｆ
ｅＢ２型複硼化物相が約６８％と鉄系合金の結合相が約
３２％からなる複硼化物系硬質合金ソースを得た。[Example] Example I Fe -10,9B -14,3Cr alloy powder: 18
．． 1%, MoB powder = 40%, pure Mo powder: 9.2%, carbonyl Ni powder: 8.4%, pure Cr powder: 1B, 7%, carbonyl Fe powder: 5.4%, graphite powder: 0. 2%, mixed and pulverized in acetone for 28 hours using a vibrating ball mill, dried, granulated, and molded, then heated at 1275°C in a vacuum.
After sintering for 20 minutes, the alloy composition of the true density was Fe-6.
B-45Mo-21,3Cr-8,4Ni, Mo2F
A complex boride hard alloy source was obtained which consisted of about 68% eB2 type complex boride phase and about 32% iron-based alloy binder phase.
実施例 ２
ＭｏＢ粉：５６．６％、純Ｍｏ粉：８％、カーボニルＮ
ｊ粉：２０．４％、純Ｃｒ粉：１５％を配合し、振動ボ
ールミルによりアセトン中で２８時時間式混合粉砕し、
乾燥・造粒・成形後、真空中１２７５℃で２０分間焼結
し、はぼ真密度の合金組成がＮｉ−６Ｂ−５８，６Ｍｏ
−１５Ｃｒの、Ｍｏ２ＮｉＢ２型複硼化物相が約７０％
とニッケル系合金の結合相が約３０％からなる複硼化物
系硬質合金ソースを得た。Example 2 MoB powder: 56.6%, pure Mo powder: 8%, carbonyl N
J powder: 20.4% and pure Cr powder: 15% were blended and mixed and ground in acetone for 28 hours using a vibrating ball mill.
After drying, granulation, and molding, sintering was performed at 1275°C in a vacuum for 20 minutes, and the alloy composition of the true density was Ni-6B-58,6Mo.
-15Cr, Mo2NiB2 type complex boride phase is about 70%
A complex boride-based hard alloy source consisting of about 30% of the binder phase of nickel-based alloy and nickel-based alloy was obtained.
実施例 ３
ＷＢ粉：６０％、純Ｃｏ粉：２５％、純Ｃｒ：１５％を
配合し、振動ボールミルによりアセトン中で２８時時間
式混合粉砕し、乾燥・造粒・成形後、真空中１２５０°
Ｃて２０分間焼結し、はぼ真密度の合金組成がＣｏ−３
，３Ｂ−５６゜７Ｗ−１５ＣｒＯＷＣｏＢ型複硼化物相
が約７８％とコバルト系合金の結合相が約２２％からな
る複硼化物系硬質合金ソースを得た。Example 3 WB powder: 60%, pure Co powder: 25%, pure Cr: 15% were blended, mixed and pulverized in acetone for 28 hours using a vibrating ball mill, dried, granulated, and molded, and then heated at 1250 mL in vacuum. °
The alloy composition of the true density was Co-3.
, 3B-56°7W-15CrOW A complex boride hard alloy source consisting of about 78% of the CoB type complex boride phase and about 22% of the cobalt alloy binder phase was obtained.
上記実施例１．２．３０本硬質合金ソースを、高周波マ
グネトロンスパッタリング装置のターゲットとして用い
、鋼材、Ｍｏ□ＦｅＢｚ系硬質合金、プラスチックフィ
ルムなどの表面にコーティング薄膜を形成させたところ
、耐摩耗、耐食性に優れた、密着性の良いコーティング
薄膜を得ることができた。なお市販のＭｏＢ粉１００％
を加圧成形後、真空中１４００℃で６０分間焼結したが
、緻密化せず十分な強度を有する硼化物系ソースを得る
ことはできなかった。The above Example 1.2.30 hard alloy sources were used as a target in a high frequency magnetron sputtering device to form a coating thin film on the surfaces of steel materials, Mo□FeBz hard alloys, plastic films, etc., resulting in wear and corrosion resistance. We were able to obtain a coating thin film with excellent adhesion. Commercially available MoB powder 100%
After pressure molding, the material was sintered in vacuum at 1400° C. for 60 minutes, but it did not become densified and a boride-based source with sufficient strength could not be obtained.
［発明の効果］
本発明の固体の複硼化物系硬質合金ソースは、工具、機
械部品、精密機械部品、プラスチックフィルＪ、などの
表面保護皮膜となる、優れた耐摩耗性、耐食性、耐久性
および組成的自由度を有するコーティング薄膜を、主と
してＰＶＤ法により形成するのに用いることができる。[Effects of the Invention] The solid complex boride hard alloy source of the present invention has excellent wear resistance, corrosion resistance, and durability, and can be used as a surface protective film for tools, machine parts, precision machine parts, plastic film J, etc. and can be used to form coating films with compositional flexibility primarily by PVD methods.
特許出願人 東洋鋼鈑株式会社 代 理 人 小林 正Patent applicant: Toyo Kohan Co., Ltd. Deputy Director Tadashi Kobayashi
Claims (5)
上の元素または合金よりなるマトリックス中に、Ｍ＿ｘ
Ｎ＿ｙＢ型（以下Ｍ，Ｎは金属、ｘ，ｙはＭ，Ｎが化合
物を形成するに必要な化学量論的な数値を表す）複硼化
物を４０〜９９重量％（以下％は重量％）含む複硼化物
系硬質合金ソース（蒸着源およびターゲット）であって
、該複硼化物において、ＭはＭｏおよび／またはＷ、Ｎ
はＦｅ，Ｃｒ，Ｃｏ，Ｎｉの中から選ばれた１種以上の
元素よりなり、該ソースに対してＢ含有量が２〜８％、
Ｍｏおよび／またはＷ含有量が（Ｍｏおよび／またはＷ
）／Ｂのモル比で０．５０〜１．５０を満足する範囲内
にあり、残部がＦｅ，Ｃｒ，Ｃｏ，Ｎｉの中から選ばれ
た１種以上の元素または合金および不可避的不純物より
なることを特徴とする複硼化物系硬質合金ソース。(1) M_x in a matrix made of one or more elements or alloys selected from Fe, Cr, Co, and Ni
N_yB type (hereinafter M and N are metals, x and y represent the stoichiometric values necessary for M and N to form a compound) complex boride at 40 to 99% by weight (hereinafter % is weight%) a complex boride-based hard alloy source (evaporation source and target) containing Mo and/or W, N in the complex boride;
is composed of one or more elements selected from Fe, Cr, Co, and Ni, and the B content is 2 to 8% with respect to the source,
Mo and/or W content is (Mo and/or W
)/B molar ratio of 0.50 to 1.50, with the remainder consisting of one or more elements or alloys selected from Fe, Cr, Co, and Ni and unavoidable impurities. A complex boride-based hard alloy source characterized by:
＿ｚＢ型（Ｍ’はＦｅ，Ｃｒ，Ｃｏ，Ｎｉ，Ｍｏ，Ｗの
中から選ばれた１種類の元素、ｚはＭ’が化合物を形成
するに必要な化学量論的な数値を表す）２元硼化物で置
換したことを特徴とする請求項１記載の複硼化物系硬質
合金ソース。(2) Less than 50% of the M_xN_yB type complex boride is M'
_zB type (M' is one type of element selected from Fe, Cr, Co, Ni, Mo, W, z represents the stoichiometric value necessary for M' to form a compound)2 The complex boride-based hard alloy source according to claim 1, characterized in that the source is substituted with an original boride.
上の元素と、Ｍｏ，Ｗ，Ｃｕ，Ｔｉ，Ｖ，Ｎｂ，Ｔａ，
Ｈｆ，Ｚｒ，Ｓｉの中から選ばれた１種以上の元素との
合金よりなるマトリックス中に、Ｍ＿ｘＮ＿ｙＢ型（以
下Ｍ，Ｎは金属、ｘ，ｙはＭ，Ｎが化合物を形成するに
必要な化学量論的な数値を表す）複硼化物を４０〜９９
重量％含む複硼化物系硬質合金ソース（蒸着源およびタ
ーゲット）であって、該複硼化物において、ＭはＭｏお
よび／またはＷとＴｉ，Ｖ，Ｎｂ，Ｔａ，Ｈｆ，Ｚｒの
中から選ばれた１種以上の元素とよりなり、ＮはＦｅ，
Ｃｒ，Ｃｏ，Ｎｉの中から選ばれた１種以上の元素より
なり、該ソースに対してＢ含有量が２〜８％、Ｍｏおよ
び／またはＷ含有量が、（Ｍｏおよび／またはＷ）／Ｂ
のモル比で０．５０〜１．５０を満足する範囲内にあり
、かつＣｕ，Ｔｉ，Ｖ，Ｎｂ，Ｔａ，Ｈｆ，Ｚｒ，Ｓｉ
の中から選ばれた１種以上の元素の合計が０．５〜２５
％、残部がＦｅ，Ｃｒ，Ｃｏ，Ｎｉの中から選ばれた１
種以上の元素または合金および不可避的不純物よりなる
ことを特徴とする複硼化物系硬質合金ソース。(3) One or more elements selected from Fe, Cr, Co, Ni, and Mo, W, Cu, Ti, V, Nb, Ta,
M_xN_yB type (hereinafter M and N are metals, x and y are M and N necessary to form a compound) in a matrix consisting of an alloy with one or more elements selected from Hf, Zr, and Si. (represents stoichiometric value) complex boride from 40 to 99
A complex boride-based hard alloy source (evaporation source and target) containing % by weight, in which M is selected from Mo and/or W and Ti, V, Nb, Ta, Hf, and Zr. N is composed of one or more elements such as Fe,
Consisting of one or more elements selected from Cr, Co, and Ni, the B content is 2 to 8% with respect to the source, and the Mo and/or W content is (Mo and/or W)/ B
The molar ratio is within the range of 0.50 to 1.50, and Cu, Ti, V, Nb, Ta, Hf, Zr, Si
The total of one or more elements selected from among 0.5 to 25
%, balance 1 selected from Fe, Cr, Co, Ni
A complex boride-based hard alloy source characterized by comprising more than one element or alloy and inevitable impurities.
＿ｚＢ型（Ｍ’はＦｅ，Ｃｒ，Ｃｏ，Ｎｉ，Ｍｏ，Ｗ，
Ｔｉ，Ｖ，Ｎｂ，Ｔａ，Ｈｆ，Ｚｒの中から選ばれた１
種類の元素、ｚはＭ’が化合物を形成するに必要な化学
量論的な数値を表す）２元硼化物で置換したことを特徴
とする請求項３記載の複硼化物系硬質合金ソース。(4) Less than 50% of the M_xN_yB type complex boride is M'
_zB type (M' is Fe, Cr, Co, Ni, Mo, W,
1 selected from Ti, V, Nb, Ta, Hf, Zr
4. The complex boride-based hard alloy source according to claim 3, characterized in that the element is substituted with a binary boride (M' is a stoichiometric value necessary for forming a compound).
またはＷ）／Ｂのモル比で０．６０〜１．４０を満足す
る範囲内にあることを特徴とする請求項１または３記載
の複硼化物系硬質合金ソース。(5) Mo and/or W content is (Mo and/
The complex boride-based hard alloy source according to claim 1 or 3, characterized in that the molar ratio of W)/B is within a range of 0.60 to 1.40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16401890A JPH0713278B2 (en) | 1990-06-25 | 1990-06-25 | Double boride type hard alloy source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16401890A JPH0713278B2 (en) | 1990-06-25 | 1990-06-25 | Double boride type hard alloy source |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0456745A true JPH0456745A (en) | 1992-02-24 |
| JPH0713278B2 JPH0713278B2 (en) | 1995-02-15 |
Family
ID=15785225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16401890A Expired - Fee Related JPH0713278B2 (en) | 1990-06-25 | 1990-06-25 | Double boride type hard alloy source |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713278B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006150461A (en) * | 2004-11-25 | 2006-06-15 | Mitsubishi Materials Kobe Tools Corp | Surface coated cemented carbide made cutting tool with hard coating layer to display excellent abrasion resistance in high speed cutting work of heat-resistant alloy |
| CN109553112A (en) * | 2018-11-12 | 2019-04-02 | 北京工业大学 | A kind of preparation method of single-phase WCoB powder |
| CN114959513A (en) * | 2022-06-23 | 2022-08-30 | 昆明理工大学 | In-situ self-generation M 3 B 2 /FeNi alloy and preparation method thereof |
-
1990
- 1990-06-25 JP JP16401890A patent/JPH0713278B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006150461A (en) * | 2004-11-25 | 2006-06-15 | Mitsubishi Materials Kobe Tools Corp | Surface coated cemented carbide made cutting tool with hard coating layer to display excellent abrasion resistance in high speed cutting work of heat-resistant alloy |
| CN109553112A (en) * | 2018-11-12 | 2019-04-02 | 北京工业大学 | A kind of preparation method of single-phase WCoB powder |
| CN109553112B (en) * | 2018-11-12 | 2022-03-22 | 北京工业大学 | Preparation method of single-phase WCoB powder |
| CN114959513A (en) * | 2022-06-23 | 2022-08-30 | 昆明理工大学 | In-situ self-generation M 3 B 2 /FeNi alloy and preparation method thereof |
| CN114959513B (en) * | 2022-06-23 | 2023-09-26 | 昆明理工大学 | In-situ autogenous M 3 B 2 FeNi alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0713278B2 (en) | 1995-02-15 |
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