JPH076023B2 - Ultra-hard composite material - Google Patents
Ultra-hard composite materialInfo
- Publication number
- JPH076023B2 JPH076023B2 JP11175988A JP11175988A JPH076023B2 JP H076023 B2 JPH076023 B2 JP H076023B2 JP 11175988 A JP11175988 A JP 11175988A JP 11175988 A JP11175988 A JP 11175988A JP H076023 B2 JPH076023 B2 JP H076023B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- composite material
- carbide
- silicon carbide
- ultra
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002131 composite material Substances 0.000 title claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 8
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 8
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 7
- 229910039444 MoC Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 description 25
- 239000011230 binding agent Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910052581 Si3N4 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
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の技術分野） 本発明は超硬質複合材料に関するものである。更に詳し
くいえば、切削工具用材料として特にすぐれた性質を有
する、炭化物を基とする超硬質複合材料に関するもので
ある。Description: TECHNICAL FIELD The present invention relates to an ultra-hard composite material. More particularly, it relates to a carbide-based superhard composite material having particularly good properties as a cutting tool material.
（従来の技術） 特に切削工具などに使用する超硬質複合材料としては、
炭化タングステンを主成分とする超硬質合金とか、炭化
チタンを主成分とするサーメット、又はアルミナを主成
分とするセラミックス等が知られている。(Prior Art) As a super-hard composite material used especially for cutting tools,
Known are superhard alloys containing tungsten carbide as a main component, cermets containing titanium carbide as a main component, and ceramics containing alumina as a main component.
さらに、超硬質合金に、TiN,TiC,Al2O3等を被覆して成
る複合材料が開発され、切削工具などの分野で実用化さ
れて来ている。Further, a composite material formed by coating a hard metal with TiN, TiC, Al 2 O 3, etc. has been developed and put to practical use in the field of cutting tools and the like.
このように、この分野において、多岐にわたって各種の
材料が開発され、又は提案されているが、その主流は炭
化タングステン−コバルト系のものが占めている。As described above, various materials have been developed or proposed in a wide variety of fields in this field, and the mainstream thereof is the tungsten carbide-cobalt-based material.
（発明が解決しようとする問題点） しかしながら、炭化タングステンやコバルトは戦略物質
であり、かつその産出国が限られており、市場が不安定
であることから、将来にわたって安定した供給を期待す
ることが難しいという問題がある。このため、これに代
る材料による超硬質材料が待望され、これを開発すべく
研究が行われている。(Problems to be solved by the invention) However, since tungsten carbide and cobalt are strategic substances and the producing countries thereof are limited and the market is unstable, expect a stable supply in the future. There is a problem that it is difficult. Therefore, an ultra-hard material as a substitute material has been long-awaited, and research has been conducted to develop it.
本発明者は、このような超硬質材料として、セラミック
ス複合材料の立場から鋭意開発研究を進めて来た。本発
明は、セラミックスを主成分とする超硬質複合材料を提
供することを目的とするものである。The inventor of the present invention has carried out earnest research and development from the standpoint of a ceramic composite material as such an ultra-hard material. An object of the present invention is to provide a super hard composite material containing ceramics as a main component.
（問題点を解決するための手段） 本発明者は、ニッケル被覆した炭化珪素ウィスカーを使
用することにより、超硬質材料としてすぐれた性質を有
する複合材料を得ることができることを見出した。(Means for Solving Problems) The present inventor has found that by using nickel-coated silicon carbide whiskers, a composite material having excellent properties as an ultra-hard material can be obtained.
炭化珪素は、窒化珪素，アルミナ，ジルコニアと並んで
４大構造材料の１つとして知られており、抜群の硬さを
有し、かつ高温強度，高温耐酸化性など高温におけるす
ぐれた物性を有しているが、一般のセラミックスにおけ
ると同様に脆く、又金属とのヌレ性が悪い。脆さという
欠点を克服するためには、靭性の大きい金属との複合材
料とすることが考えられるが、金属中に炭化珪素粒子を
分散させても、結合相との付着性が悪いため、たとえば
切削工具用材料として使用する場合、刃先が欠損するな
どの問題がある。Silicon carbide is known as one of the four major structural materials, along with silicon nitride, alumina, and zirconia, and has outstanding hardness and excellent physical properties at high temperatures such as high temperature strength and high temperature oxidation resistance. However, it is brittle like general ceramics and has poor wettability with metals. In order to overcome the drawback of brittleness, it is possible to use a composite material with a metal having high toughness, but even if silicon carbide particles are dispersed in the metal, the adhesion with the binder phase is poor, so When it is used as a material for a cutting tool, there is a problem that the cutting edge is broken.
本発明者は、このような、炭化珪素のもろさを改善し、
しかも結合相との付着性を改善し、切削工具用材料とし
て利用する場合に何等問題の起らない材料を得るために
は、前述したような、ニッケルで被覆した炭化珪素ウィ
スカーを使用することが非常に効果的であることを見出
し本発明を完成するに至った。The present inventors have improved such brittleness of silicon carbide,
Moreover, in order to improve the adhesion to the binder phase and obtain a material that does not cause any problems when used as a material for a cutting tool, it is necessary to use the silicon carbide whiskers coated with nickel as described above. They have found that they are very effective and have completed the present invention.
すなわち、本発明は、 ニッケルで被覆した炭化珪素ウィスカー :10〜40重量％ 炭化チタン :10〜50重量％ 炭化モリブデン :5〜30重量％ 炭化タングステン :5〜20重量％ ニッケル又はニッケルの50重量％以下をコバルトで置換
したもの :10〜50重量％ から成ることを特徴とする超硬質複合材料に関するもの
である。That is, the present invention is a silicon carbide whiskers coated with nickel: 10 to 40 wt% titanium carbide: 10 to 50 wt% molybdenum carbide: 5 to 30 wt% tungsten carbide: 5 to 20 wt% nickel or 50 wt% of nickel The present invention relates to an ultra-hard composite material, characterized in that the following is substituted with cobalt: 10 to 50% by weight.
ニッケルで被覆した炭化珪素ウィスカーを使用する前記
の超硬質複合材料は、すぐれた硬さを有し、高温強度，
高温耐酸化性など高温における物性がすぐれている外、
もろさが改善され、切削工具材料として使用した場合に
おいても、鋼切削寿命時間，抗折力などの諸性質もすぐ
れたものとなる。しかも、ニッケルで被覆した炭化珪素
ウィスカーを使用することにより、結合相のニッケル又
はニッケル−コバルトとの結合力が強固となる。このた
め、従来、炭化珪素を含む材料においては困難とされて
いた、切削工具材料用途においても十分活用できるもの
となる外、各種超硬質材料、たとえば耐摩耗性材料，耐
熱性材料などの用途にも使用可能な材料が得られる。The above-mentioned super-hard composite material using nickel-coated silicon carbide whiskers has excellent hardness, high temperature strength,
In addition to excellent physical properties at high temperature such as high temperature oxidation resistance,
The brittleness is improved, and even when used as a cutting tool material, various properties such as steel cutting life time and transverse rupture strength are excellent. Moreover, the use of the silicon carbide whiskers coated with nickel strengthens the binding force with nickel or nickel-cobalt in the binding phase. Therefore, in addition to being able to be sufficiently utilized for cutting tool material applications, which has been conventionally difficult for materials containing silicon carbide, it can be used for various super hard materials such as wear resistant materials and heat resistant materials. Also a usable material is obtained.
表面にニッケル被覆を形成させるべき炭化珪素ウィスカ
ーは、α型，β型またはα／β混合型のいずれの結晶形
を有するものでもよく、平均径が５μｍ以下、平均長さ
が10〜100μｍのものが適当である。このような炭化珪
素ウィスカーの表面上に、２μｍ以下の厚さの被覆を形
成させたものを使用する。被覆を形成する方法は特定の
方法でなければならない理由はない。たとえば、通常の
無電解メッキ方法などによって被覆を形成することがで
きる。The silicon carbide whiskers on which the nickel coating is to be formed may have any of α-type, β-type or α / β-mixed crystal form, and have an average diameter of 5 μm or less and an average length of 10 to 100 μm. Is appropriate. The surface of such a silicon carbide whisker having a coating with a thickness of 2 μm or less is used. There is no reason why the method of forming the coating must be specific. For example, the coating can be formed by a conventional electroless plating method or the like.
ニッケルで被覆した炭化珪素ウィスカーを前述の割合
（重量％、以下単に％で示す）で炭化チタン，炭化モリ
ブデン，炭化タングステン，ニッケル又はニッケルを50
％以下コバルトで置換したものと混合する。得られた混
合物を成形後たとえばホットプレスにより通常は1300〜
1500℃の範囲内で加熱焼成することにより本発明の超硬
質複合材料を得る。The silicon carbide whiskers coated with nickel are mixed with titanium carbide, molybdenum carbide, tungsten carbide, nickel or nickel in the above-mentioned proportion (weight%, hereinafter simply referred to as%).
% Or less Mixed with cobalt substituted. After molding the obtained mixture is usually 1300 ~ by hot pressing, for example.
The superhard composite material of the present invention is obtained by heating and firing in the range of 1500 ° C.
なお、炭化チタン，炭化モリブダン，炭化タングステ
ン，ニッケル，コバルトは平均粒径0.5〜２μｍのもの
を使用するのが好ましい。In addition, it is preferable to use titanium carbide, molybdenum carbide, tungsten carbide, nickel, and cobalt having an average particle diameter of 0.5 to 2 μm.
ニッケルで被覆した炭化珪素ウィスカーは、10〜40％の
範囲内でなければならない。10％を下回ると添加効果が
少く、特に高温強度が低下する。一方40％を超えると、
靭性が低下するため好ましくない。炭化チタンは10〜50
％の範囲内におさめる。炭化チタンは、、炭化珪素ウィ
スカーと共に、本素材の母材を構成するもので、抜群の
硬さを有するものであり、10％より少い量では十分な硬
度が得られず、一方50％を超えると靭性の低下が目立
ち、いずれも好ましくない。炭化モリブデンは５〜30％
の添加量とする。炭化モリブデンは炭化物の粒成長を抑
制し、かつ炭化物とニッケル，コバルトとの間のヌレ性
改善に寄与する。５％より少ないときは添加効果が少な
く、30％を超えると、硬度の低下が見られる。又炭化タ
ングステンを５〜20％添加するのは、焼結性を向上させ
るためである。Nickel coated silicon carbide whiskers should be in the range of 10-40%. If it is less than 10%, the effect of addition is small, and particularly the high temperature strength decreases. On the other hand, if it exceeds 40%,
It is not preferable because the toughness decreases. 10 to 50 for titanium carbide
Keep it within the range of%. Titanium carbide, which, together with silicon carbide whiskers, constitutes the base material of this material, has outstanding hardness, and if it is less than 10%, sufficient hardness cannot be obtained. If it exceeds the above range, the toughness is conspicuously deteriorated, which is not preferable. 5-30% molybdenum carbide
And the addition amount. Molybdenum carbide suppresses the grain growth of carbide and contributes to the improvement of the wettability between the carbide and nickel or cobalt. If it is less than 5%, the effect of addition is small, and if it exceeds 30%, the hardness is lowered. The addition of 5 to 20% of tungsten carbide is for improving the sinterability.
本発明の超硬質複合材料において、ニッケル単独、又は
その50％以下をコバルトで置換したものを結合相とす
る。結合相の割合は10〜50％の範囲とするのが適当であ
り、結合相が10％より減少すると靭性の低下を来すこと
となり好ましくない。一方50％を超えると硬度が低下す
る傾向がありやはり好ましくない。このため、結合相の
割合は10〜50％の範囲内とすることが好ましい。結合相
におけるニッケルの50％以下をコバルトで置換すること
が可能であるが、10〜50％程度にとどめるのが好まし
い。In the super-hard composite material of the present invention, nickel is used alone or 50% or less thereof is replaced with cobalt to form a binder phase. The proportion of the binder phase is appropriately in the range of 10 to 50%, and if the binder phase is less than 10%, the toughness will be deteriorated, which is not preferable. On the other hand, if it exceeds 50%, the hardness tends to decrease, which is also not preferable. Therefore, the proportion of the binder phase is preferably in the range of 10 to 50%. It is possible to replace 50% or less of nickel in the binder phase with cobalt, but it is preferable to keep it to about 10 to 50%.
（実 施 例） 次に具体的な実施例を記載することにより本発明を更に
詳細に説明する。(Examples) Next, the present invention will be described in more detail by describing specific examples.
（実施例１〜８、比較例１〜３） 第１表に示した各種材料を、同表に示した割合（％）で
混合した。(Examples 1 to 8 and Comparative Examples 1 to 3) The various materials shown in Table 1 were mixed in the proportions (%) shown in the table.
炭化珪素ウィスカーは、平均径３μｍ、平均長さ50μｍ
の市販品のα／β混合型を使用し、その表面上に、塩化
ニッケル，次亜燐酸ソーダ，及びクエン酸等を含有する
液を使用して無電解メッキにより0.1〜１μｍの厚さの
ニッケル被覆を形成した。このニッケル被覆炭化珪素ウ
ィスカーをトルエンで分散，過して混合用試料とし
た。Silicon carbide whiskers have an average diameter of 3 μm and an average length of 50 μm
The commercially available α / β mixed type is used, and nickel having a thickness of 0.1 to 1 μm is formed on the surface by electroless plating using a solution containing nickel chloride, sodium hypophosphite, citric acid and the like. A coating was formed. The nickel-coated silicon carbide whiskers were dispersed in toluene and filtered to prepare a sample for mixing.
炭化チタン，炭化モリブデン及び炭化タングステンの各
種炭化物及びニッケル又はコバルトは、それぞれ、平均
粒径1.0〜1.3μｍの市販品を使用した。As the various carbides of titanium carbide, molybdenum carbide and tungsten carbide and nickel or cobalt, commercially available products having an average particle size of 1.0 to 1.3 μm were used, respectively.
炭化物及び金属原料を第１表に示した割合（％）に配合
し、トルエンに分散し、ボールミルで３日間粉砕混合し
た後、前述のニッケル被覆炭化珪素ウィスカーと混合し
た。Carbides and metal raw materials were mixed in the proportions (%) shown in Table 1, dispersed in toluene, pulverized and mixed in a ball mill for 3 days, and then mixed with the above nickel-coated silicon carbide whiskers.
このようにして得た混合物を乾燥し、１トン/cm2でシン
グルプッシュ方式で成形した後1.5トン/cm2でCIP成形を
行った。成形体をホットプレスで1450℃,200kg/cm2の条
件下で、真空雰囲気中で１時間保持して焼結した。Thus dried-obtained mixture was subjected to CIP molding at 1.5 tons / cm 2 after forming a single push method in 1 ton / cm 2. The compact was sintered by hot pressing under conditions of 1450 ° C. and 200 kg / cm 2 in a vacuum atmosphere for 1 hour.
得られた焼結体をSNGN432型（CIS規格）の切削チップに
加工した。この切削チップについて、それぞれの切刃の
逃げ面摩耗幅0.2mm基準で寿命時間を測定した。この測
定結果をあわせて第１表にまとめて示す。この測定条件
は下記のとおりである。The obtained sintered body was processed into a cutting tip of SNGN432 type (CIS standard). The life of the cutting tip was measured based on the flank wear width of each cutting edge being 0.2 mm. The results of this measurement are shown together in Table 1. The measurement conditions are as follows.
被削材 FCD45 切削速度 250m/分 切り込み 1.5mm 送り速度 0.3mm/rev. 実施例及び比較例の結果が示すとおり、本発明におい
て、ニッケル被覆を施した炭化珪素を所定の組成範囲で
使用して得た硬質複合材料は、比較例に示される如き材
料に比べ、すぐれた切削部材としての性質を有する。Work material FCD45 Cutting speed 250 m / min Depth of cut 1.5 mm Feed speed 0.3 mm / rev. As shown by the results of Examples and Comparative Examples, in the present invention, the hard composite material obtained by using nickel-coated silicon carbide in the predetermined composition range is superior to the materials as shown in Comparative Examples. It has properties as a cutting member.
（発明の効果） 本発明により、すぐれた切削性能を有する複合材料を提
供することが可能となった。(Effects of the Invention) The present invention makes it possible to provide a composite material having excellent cutting performance.
本発明の超硬質複合材料は、切削部材としての用途の
外、耐摩耗性材料例えば精密工作機械部材材料、あるい
は耐熱性材料例えば熱交換機，ガスタービン部材として
の用途にも使用することができるすぐれた材料である。The super-hard composite material of the present invention can be used not only as a cutting member but also as a wear resistant material such as a precision machine tool member material, or a heat resistant material such as a heat exchanger or a gas turbine member. It is a material.
Claims (1)
0〜40重量％ 炭化チタン :10〜50重量％ 炭化モリブデン :5〜30重量％ 炭化タングステン :5〜20重量％ ニッケルまたはニッケルの50重量％以下をコバルトで置
換したもの :10〜50重量％ から成ることを特徴とする超硬質複合材料。1. Silicon carbide whiskers coated with nickel: 1
0-40% by weight Titanium carbide: 10-50% by weight Molybdenum carbide: 5-30% by weight Tungsten carbide: 5-20% by weight Nickel or nickel with 50% by weight or less replaced by cobalt: From 10-50% by weight A super-hard composite material characterized by being formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11175988A JPH076023B2 (en) | 1988-05-09 | 1988-05-09 | Ultra-hard composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11175988A JPH076023B2 (en) | 1988-05-09 | 1988-05-09 | Ultra-hard composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01283331A JPH01283331A (en) | 1989-11-14 |
| JPH076023B2 true JPH076023B2 (en) | 1995-01-25 |
Family
ID=14569470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11175988A Expired - Lifetime JPH076023B2 (en) | 1988-05-09 | 1988-05-09 | Ultra-hard composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH076023B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116024451A (en) * | 2022-12-12 | 2023-04-28 | 河南大地合金有限公司 | Titanium diboride whisker alloy preparation method and alloy |
-
1988
- 1988-05-09 JP JP11175988A patent/JPH076023B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01283331A (en) | 1989-11-14 |
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