JPH07207381A - Production of particle reinforced composite material - Google Patents
Production of particle reinforced composite materialInfo
- Publication number
- JPH07207381A JPH07207381A JP4257293A JP25729392A JPH07207381A JP H07207381 A JPH07207381 A JP H07207381A JP 4257293 A JP4257293 A JP 4257293A JP 25729392 A JP25729392 A JP 25729392A JP H07207381 A JPH07207381 A JP H07207381A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- composite material
- ultrafine particles
- mixture
- particles
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 28
- 239000011208 reinforced composite material Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 150000004767 nitrides Chemical class 0.000 claims abstract description 10
- 238000010891 electric arc Methods 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 239000011882 ultra-fine particle Substances 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012495 reaction gas Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- -1 respectively Substances 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 21
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910018575 Al—Ti Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910007880 ZrAl Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011225 non-oxide ceramic Substances 0.000 description 2
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 235000007575 Calluna vulgaris Nutrition 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属マトリックス中に微
細なセラミックス粒子が分散してなる粒子強化複合材を
製造する方法に関し、特に、窒化チタン超微粒子とAl3
Ti相とがアルミニウムマトリックス中に分散した複合材
を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a particle-reinforced composite material in which fine ceramic particles are dispersed in a metal matrix, and in particular, titanium nitride ultrafine particles and Al 3
The present invention relates to a method for producing a composite material in which a Ti phase is dispersed in an aluminum matrix.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】航空機
材料をはじめとする各種耐熱材料として、また、高強度
が要求される構造用材料として、各種合金、金属間化合
物、金属とセラミックスの複合材等の新材料の開発が精
力的に行われている。2. Description of the Related Art Various alloys, intermetallic compounds, and composite materials of metals and ceramics are used as various heat-resistant materials such as aircraft materials and as structural materials requiring high strength. The development of new materials such as
【０００３】その中で、金属とセラミックスとの複合材
としては、たとえばTi、Ni、Al等を含む合金中に、耐熱
性を示す無機酸化物を分散した酸化物粒子分散合金（Ｏ
ＤＳ）等が知られている。また、酸化物粒子に変えて、
非酸化物系のセラミックス（窒化物、炭化物、ホウ化物
等）粒子を用い、これを合金中に分散した複合材の開発
も行われている。Among them, as a composite material of metal and ceramics, for example, an oxide particle dispersion alloy (O) in which a heat-resistant inorganic oxide is dispersed in an alloy containing Ti, Ni, Al, etc.
DS) and the like are known. Also, change to oxide particles,
Development of a composite material in which non-oxide ceramic particles (nitride, carbide, boride, etc.) particles are used and dispersed in an alloy is also under way.
【０００４】上述したような金属（合金）とセラミック
ス粒子との複合材は、一般に、マトリックスとなる金属
の粉末とセラミックス粒子とを用い、いわゆる粉末冶金
の方法にしたがって製造される。しかしながら、この種
の方法で良好な強度を有する複合材を得るためには、10
00℃を超す温度でＨＩＰ法やホットプレス法等を行わな
ければならず、製造プロセスが複雑となりコストも高く
つく。また、合金中の粒子の分散状態を均一にするのも
難しい。The above-mentioned composite material of metal (alloy) and ceramic particles is generally manufactured by using a powder of metal serving as a matrix and ceramic particles according to a so-called powder metallurgy method. However, in order to obtain a composite having good strength by this kind of method, 10
The HIP method and the hot pressing method have to be performed at a temperature higher than 00 ° C, which makes the manufacturing process complicated and the cost is high. It is also difficult to make the dispersed state of the particles in the alloy uniform.
【０００５】特に、非酸化物系セラミックスの中で人工
的に製造されたものを強化粒子として用いた場合には、
この強化粒子とマトリックスとなる合金との化学的、力
学的な適合性の問題（たとえば、粒子とマトリックスと
の反応性の問題、粒子とマトリックスの界面における接
合強度の問題、粒子とマトリックスの熱膨張率の違いに
起因する複合材の強度の問題等）が生じやすい。また、
凝集や偏析の問題も起こりやすい。Particularly, when artificially manufactured non-oxide ceramics are used as the reinforcing particles,
Chemical and mechanical compatibility issues between this strengthening particle and the matrix alloy (eg, particle-matrix reactivity issues, bond strength problems at the particle-matrix interface, thermal expansion of the particles and matrix). Problems such as the strength of the composite material due to the difference in the ratio) are likely to occur. Also,
Problems such as aggregation and segregation are also likely to occur.
【０００６】したがって、本発明の目的は、高強度かつ
高硬度で、構造材料として使用することができる粒子強
化複合材を容易に製造することができる方法を提供する
ことである。Therefore, an object of the present invention is to provide a method capable of easily producing a particle-reinforced composite material having high strength and high hardness, which can be used as a structural material.
【０００７】[0007]
【課題を解決するための手段】上記目的に鑑み鋭意研究
の結果、本発明者は、複合材においてマトリックスを形
成する金属の超微粒子と、他の金属の窒化物、炭化物、
ホウ化物のいずれかからなる超微粒子とを含有する混合
物を用い、この超微粒子の混合物を所望の形状に成形し
たのち、マトリックスとなる金属の融点以上の温度で熱
処理すれば、良好な強度及び高い硬度を有する複合材と
することができることを発見し、本発明を完成した。As a result of earnest research in view of the above object, the present inventor has found that ultrafine particles of a metal forming a matrix in a composite material, and nitrides and carbides of other metals,
Using a mixture containing ultrafine particles made of any of boride and molding the mixture of the ultrafine particles into a desired shape, and then heat-treating at a temperature equal to or higher than the melting point of the metal forming the matrix, good strength and high The present invention has been completed by discovering that a composite material having hardness can be obtained.
【０００８】すなわち、粒子強化複合材を製造する本発
明の方法は、(a) 第一の金属からなる第一の超微粒子
と、第二の金属の窒化物、炭化物、又はホウ化物のいず
れかからなる第二の超微粒子との混合物を製造し、(b)
前記混合物から成形体を作製し、(c) 前記成形体を前記
第一の金属の融点以上の温度で熱処理することにより、
前記第一の金属と前記第二の金属からなる金属間化合物
を生じさせ、もって、前記第一の金属からなるマトリッ
クス中に、前記金属間化合物からなる相と、前記第二の
超微粒子とを分散した粒子強化複合材とすることを特徴
とする。That is, the method of the present invention for producing a particle-reinforced composite material comprises (a) a first ultrafine particle composed of a first metal and a nitride, a carbide, or a boride of a second metal. Producing a mixture with a second ultrafine particle consisting of (b)
A molded body is produced from the mixture, and (c) the molded body is heat-treated at a temperature equal to or higher than the melting point of the first metal,
An intermetallic compound composed of the first metal and the second metal is produced, and thus, in a matrix composed of the first metal, a phase composed of the intermetallic compound and the second ultrafine particles are formed. It is characterized in that it is a dispersed particle-reinforced composite material.
【０００９】本発明の好ましい態様では、前記第一の金
属と前記第二の金属とからなる合金に対して反応ガス中
でプラズマアーク放電を行うことにより、第一の超微粒
子と第二の超微粒子との混合物を製造し、これに対して
上述の方法を適用する。In a preferred embodiment of the present invention, the first ultrafine particles and the second ultrafine particles are formed by performing plasma arc discharge on the alloy composed of the first metal and the second metal in a reaction gas. A mixture with microparticles is produced, to which the above-mentioned method is applied.
【００１０】以下、本発明を詳細に説明する。本発明の
方法によれば、金属窒化物、金属炭化物、金属ホウ化物
のいずれかの超微粒子を均一に分散した粒子強化複合材
を製造することができるが、以下においては、窒化チタ
ンの超微粒子をアルミニウムマトリックス中に分散した
粒子強化複合材の製造方法を例にとり、本発明を詳細に
説明する。なお、本明細書における「超微粒子」とは、
平均粒径が0.03〜0.07μｍ程度のものを指す。Hereinafter, the present invention will be described in detail. According to the method of the present invention, it is possible to produce a particle-reinforced composite material in which ultrafine particles of any one of metal nitride, metal carbide and metal boride are uniformly dispersed. The present invention will be described in detail by taking as an example a method for producing a particle-reinforced composite material in which is dispersed in an aluminum matrix. The "ultrafine particles" in the present specification mean
The average particle size is about 0.03 to 0.07 μm.
【００１１】まず、金属アルミニウムの超微粒子と、窒
化チタンの超微粒子との混合物を製造する。この混合物
は、以下に述べる窒素プラズマ−蒸発金属反応法により
製造することができる。First, a mixture of ultrafine particles of metallic aluminum and ultrafine particles of titanium nitride is produced. This mixture can be produced by the nitrogen plasma-vaporized metal reaction method described below.
【００１２】窒素プラズマ−蒸発金属反応法とは、窒素
ガス中で、金属（又は合金）に対してプラズマアーク放
電を行い、窒素プラズマを生成すると同時に、金属（又
は合金）を蒸発させ、金属蒸気と窒素プラズマとを反応
させる方法である。以下、具体的にこれを説明する。The nitrogen plasma-evaporation metal reaction method is a plasma vapor discharge of a metal (or alloy) in nitrogen gas to generate nitrogen plasma and at the same time evaporate the metal (or alloy) to produce a metal vapor. And nitrogen plasma are reacted. This will be specifically described below.
【００１３】まず、アルミニウム−チタン合金を製造す
る。AlとTiとの比（原子％における比）は40：60〜60：
40とするのが好ましい。Tiの割合が４０原子％未満であ
ると、窒素プラズマ−蒸発金属反応法によって得られる
生成物中の窒化チタンの割合が少なくなる。一方、Tiの
割合を６０原子％を超す量とすると、生成物中のアルミ
ニウムの量が少なくなる。すなわち、最終的に得られる
複合材のマトリックスの量が減少し、良好な複合材とす
ることができない。First, an aluminum-titanium alloy is manufactured. The ratio of Al to Ti (ratio in atomic%) is 40:60 to 60 :.
It is preferably 40. When the proportion of Ti is less than 40 atomic%, the proportion of titanium nitride in the product obtained by the nitrogen plasma-vapor metal reaction method becomes small. On the other hand, if the proportion of Ti exceeds 60 atomic%, the amount of aluminum in the product will be small. That is, the amount of matrix of the finally obtained composite material is reduced, and a good composite material cannot be obtained.
【００１４】上記の合金はアーク溶解法等により製造す
ることができる。アーク溶解法では、上述の配合比とな
るように金属アルミニウムと金属チタンとを秤量して混
合し、得られた混合物に対して不活性ガス中でアーク放
電を行い、溶融して合金化する。得られた合金はペレッ
ト状、ボタン状等に成形して用いることができる。The above alloy can be manufactured by an arc melting method or the like. In the arc melting method, metal aluminum and metal titanium are weighed and mixed so as to have the above-mentioned mixing ratio, and the obtained mixture is subjected to arc discharge in an inert gas to melt and alloy. The obtained alloy can be molded into pellets, buttons or the like for use.
【００１５】次に、図１に示す装置に上記合金を設置し
て窒素プラズマ−蒸発金属反応法を実施する。ここで、
装置１は、上部チャンバー２と下部チャンバー３とを有
し、上部チャンバー２には合金12を設置するヒース４が
設けられている。ヒース４の上にはアーク電極５が備え
られている。また、上部チャンバー２には反応ガス（窒
素ガス）を取り入れるガス注入口６が設けられている。
なお、アーク電極５としては、Ｗ、Mo、Ta、Ti等を用い
ることができる。Next, the above alloy is installed in the apparatus shown in FIG. 1 and the nitrogen plasma-evaporation metal reaction method is carried out. here,
The apparatus 1 has an upper chamber 2 and a lower chamber 3, and the upper chamber 2 is provided with a heath 4 for mounting an alloy 12. An arc electrode 5 is provided on the heath 4. Further, the upper chamber 2 is provided with a gas inlet 6 for taking in a reaction gas (nitrogen gas).
As the arc electrode 5, W, Mo, Ta, Ti or the like can be used.
【００１６】一方、下部チャンバー３には、得られる超
微粒子を捕集するダイス８が配置されている。また、下
部チャンバー３には、チャンバー内を排気（減圧）する
排気口９が形成されている。On the other hand, a die 8 for collecting the obtained ultrafine particles is arranged in the lower chamber 3. Further, the lower chamber 3 is formed with an exhaust port 9 for exhausting (decompressing) the inside of the chamber.
【００１７】上部チャンバー２と下部チャンバー３とは
管10のみにより連通しており、管10の下部チャンバー３
側にはノズル11が取り付けられている。ノズル11はダイ
ス８の凹部内に向けられている。一方、管10の上部チャ
ンバー２側の開口端部は比較的広口に形成されており、
ヒース４の斜め上に口部を向けている。The upper chamber 2 and the lower chamber 3 are communicated with each other only by the pipe 10, and the lower chamber 3 of the pipe 10 is connected.
A nozzle 11 is attached to the side. The nozzle 11 is directed into the recess of the die 8. On the other hand, the opening end of the tube 10 on the upper chamber 2 side is formed with a relatively wide mouth,
The mouth is directed diagonally above the heather 4.
【００１８】図１に示すように、装置１の上部チャンバ
ー２内のヒース４に合金12を設置し、排気口９から吸引
して上下チャンバー内を減圧する。減圧は両チャンバー
内の圧力が１×10-4Torr程度となるまで行うのが好まし
い。As shown in FIG. 1, the alloy 12 is placed on the heath 4 in the upper chamber 2 of the apparatus 1 and sucked from the exhaust port 9 to reduce the pressure in the upper and lower chambers. The pressure reduction is preferably performed until the pressure in both chambers reaches about 1 × 10 −4 Torr.
【００１９】次に、一旦排気口９側のバルブ（図示せ
ず）を閉じ、ガス注入口６から窒素ガスを上部チャンバ
ー２内に導入する。ある程度の窒素ガス（３００Torr以
上の圧力となる窒素ガス）が上部チャンバー２内に入っ
た時点で、排気口９側のバルブを少し開ける。ここで、
ノズル11の内径を0.5 〜2.0 mm程度に細く形成しておけ
ば、排気口９からの排気量と、ガス注入口６からの窒素
ガスの導入量とを調節することにより、上部チャンバー
２内の窒素ガス圧を300 〜600 Torr程度に保ちながら
（いわゆる定常状態にしながら）、上部チャンバー２と
下部チャンバー３との間に圧力差を生じさせることがで
きる。Next, the valve (not shown) on the exhaust port 9 side is once closed, and nitrogen gas is introduced into the upper chamber 2 through the gas injection port 6. When a certain amount of nitrogen gas (nitrogen gas having a pressure of 300 Torr or more) enters the upper chamber 2, the valve on the exhaust port 9 side is slightly opened. here,
If the inner diameter of the nozzle 11 is made thin to about 0.5 to 2.0 mm, the amount of exhaust gas from the exhaust port 9 and the amount of nitrogen gas introduced from the gas injection port 6 can be adjusted to control the inside of the upper chamber 2. It is possible to generate a pressure difference between the upper chamber 2 and the lower chamber 3 while maintaining the nitrogen gas pressure at about 300 to 600 Torr (while maintaining a so-called steady state).
【００２０】上部チャンバー２内の窒素ガス圧を上記範
囲に保った状態で、１００〜３００Ａのアーク電流で合
金12をアーク加熱し、これを溶融する。これにより、合
金12からアルミニウム及びチタンの蒸気が発生するが、
このとき、同時に窒素プラズマも生じる。With the nitrogen gas pressure in the upper chamber 2 maintained within the above range, the alloy 12 is arc-heated with an arc current of 100 to 300 A to melt it. This will generate aluminum and titanium vapors from alloy 12,
At this time, nitrogen plasma is also generated at the same time.
【００２１】アルミニウム蒸気、チタン蒸気のそれぞれ
と窒素プラズマとが反応し、超微粒子の窒化アルミニウ
ム及び窒化チタンが生成される。上述の通り、上下チャ
ンバー間には圧力差があるので、上部チャンバー２内で
生成された超微粒子は管10を通って下部チャンバー３に
流入する。ノズル11の内径が小さいので、超微粒子はノ
ズル11から噴出し、ダイス８の凹部内に堆積する。Each of aluminum vapor and titanium vapor reacts with nitrogen plasma to produce ultrafine particles of aluminum nitride and titanium nitride. As described above, since there is a pressure difference between the upper and lower chambers, the ultrafine particles generated in the upper chamber 2 flow into the lower chamber 3 through the tube 10. Since the inner diameter of the nozzle 11 is small, the ultrafine particles are ejected from the nozzle 11 and are deposited in the concave portion of the die 8.
【００２２】生成された超微粒子（堆積物）中には、窒
化アルミニウム、窒化チタンの他に、アルミニウムの超
微粒子も含まれる。図２は用いたAl−Ti合金中のAlとTi
の比と、得られる超微粒子（堆積物）中のAl、AlＮ及び
TiＮの各超微粒子の体積分率を示すグラフである。あら
かじめ、予備試験により図２に示すようなグラフを作成
しておけば、合金の組成を変化させることにより、堆積
物中のAl、AlＮ及びTiＮの各超微粒子の割合を容易に調
節することができる。The ultrafine particles (deposit) produced include aluminum ultrafine particles in addition to aluminum nitride and titanium nitride. Figure 2 shows Al and Ti in the Al-Ti alloy used.
Ratio of Al, AlN and ultrafine particles (sediment) obtained
It is a graph which shows the volume fraction of each ultrafine particle of TiN. If a graph such as that shown in FIG. 2 is prepared in advance by a preliminary test, the ratio of the ultrafine particles of Al, AlN and TiN in the deposit can be easily adjusted by changing the composition of the alloy. it can.
【００２３】Al、AlＮ及びTiＮの各超微粒子の好ましい
割合は、体積分率でAl：AlＮ：TiＮ＝４０〜７０：２０
〜５０：５〜１０である。さらに好ましくはAl：AlＮ：
TiＮ＝６０〜７０：２０〜３０：５〜１０である。A preferable ratio of the ultrafine particles of Al, AlN and TiN is Al: AlN: TiN = 40 to 70:20 in terms of volume fraction.
-50: 5-10. More preferably Al: AlN:
TiN = 60 to 70:20 to 30: 5 to 10.
【００２４】なお、本発明では、必ずしも上述した方法
で超微粒子状のAl、AlＮ及びTiＮ混合物を製造する必要
はなく、Al超微粒子と、TiＮ超微粒子とを別工程で製造
し、これを均一に混合して用いることもできる。しかし
ながら、超微粒子同士の均一な混合と、製造プロセスの
簡略化を考えると、上述の方法で超微粒子状のAl、AlＮ
及びTiＮ混合物を製造するのが好ましい。In the present invention, it is not always necessary to produce the ultrafine-particle mixture of Al, AlN, and TiN by the above-mentioned method, but the Al ultrafine particles and the TiN ultrafine particles are produced in separate steps, and the resulting mixture is homogenized. It can also be used as a mixture. However, considering the uniform mixing of the ultrafine particles and the simplification of the manufacturing process, the ultrafine particles of Al and AlN can be formed by the above method.
And TiN mixtures are preferably produced.
【００２５】Al−AlＮ−TiＮの超微粒子混合物を得たな
ら、これを圧粉成形する。圧粉成形は、真空中で３００
ＭPa〜１ＧPa程度の圧力で行うのが好ましい。窒素プラ
ズマ−蒸発金属反応法で用いたダイスをそのまま用いれ
ば、ペレット状物、柱状物（棒状物）等の成形体が簡単
に得られる。なお、成形体の形状は種々変更することが
できる。Once the ultrafine Al-AlN-TiN mixture has been obtained, it is compacted. For powder compaction, 300 in vacuum
It is preferable to carry out at a pressure of about MPa to 1 GPa. If the die used in the nitrogen plasma-evaporation metal reaction method is used as it is, a molded product such as a pellet or a column (rod) can be easily obtained. The shape of the molded body can be variously changed.
【００２６】成形体を４００〜６５０℃、５０〜300 Ｍ
Paの条件でホットプレスする。ホットプレスの時間は３
０〜６０分とするのが好ましい。また、ホットプレスは
１×10-5Torr以下の真空下で行うのが好ましい。The molded body is heated to 400 to 650 ° C. and 50 to 300 M.
Hot press under Pa condition. Hot press time is 3
It is preferably 0 to 60 minutes. The hot pressing is preferably performed under a vacuum of 1 × 10 −5 Torr or less.
【００２７】得られた焼結体をアルミニウムの融点以上
で熱処理する。好ましくはAlの融点〜800 ℃、より好ま
しくは700 〜750 ℃で熱処理する。熱処理時間は１〜10
時間とするのが好ましい。この熱処理も１×10-5Torr以
下の真空下で行うのが好ましい。なお、上記熱処理条件
でホットプレスを行えば、焼結と同時に熱処理も行うこ
とができる。The obtained sintered body is heat-treated at a temperature above the melting point of aluminum. The heat treatment is preferably performed at a melting point of Al to 800 ° C, more preferably 700 to 750 ° C. Heat treatment time is 1-10
Preferably, it is time. This heat treatment is also preferably performed under a vacuum of 1 × 10 −5 Torr or less. If hot pressing is performed under the above heat treatment conditions, heat treatment can be performed simultaneously with sintering.
【００２８】上述の熱処理により、焼結体内においてAl
とTiＮとが反応し、金属間化合物であるAl3 Tiが生成
し、アルミニウムマトリックス中に、Al3 Ti相とTiＮ粒
子とが分散した複合材が得られる。By the above heat treatment, Al in the sintered body
And TiN react with each other to form Al 3 Ti which is an intermetallic compound, and a composite material in which an Al 3 Ti phase and TiN particles are dispersed in an aluminum matrix is obtained.
【００２９】Al3 Tiは高い硬度を有し、また耐熱性、耐
酸化性にも優れている。したがって、Al3 Ti相が系内に
分散してなる複合材は高硬度、高耐熱性、高耐酸化性を
有することになる。特に、窒素プラズマ−蒸発金属反応
法による超微粒子の混合物を用いて得られた複合材は、
Al3 Ti相が複合材内に均一に分散して形成されるので、
良好な物性を有する。Al 3 Ti has a high hardness and is also excellent in heat resistance and oxidation resistance. Therefore, the composite material in which the Al 3 Ti phase is dispersed in the system has high hardness, high heat resistance, and high oxidation resistance. In particular, the composite material obtained by using a mixture of ultrafine particles by the nitrogen plasma-vapor metal reaction method,
Since the Al 3 Ti phase is uniformly dispersed and formed in the composite material,
It has good physical properties.
【００３０】Al3 Ti相は、溶融状態のAlがTiＮ粒子内に
拡散することにより生じるものと考えられる。ここで、
図３に模式的に示すように、AlとTiＮとAlＮとからなる
焼結体20を上述の条件で熱処理した場合、(a) 焼結体20
中のTiＮ粒子21の表層部に、金属間化合物であるAl3 Ti
の相が形成され、複相の粒子22が形成されるか、又は
(b) TiＮ粒子自身がAl3 Ti粒子23に変化するかは必ずし
も明らかではないが、いずれにせよ、アルミニウムマト
リックス中にAl3 Ti相が分散した組織が得られる。な
お、上記(a) 、(b) のいずれの場合においても、得られ
る複合材中には未反応のTiＮ超微粒子21が残存する。It is considered that the Al 3 Ti phase is generated by the diffusion of molten Al into the TiN particles. here,
As shown schematically in FIG. 3, when the sintered body 20 composed of Al, TiN, and AlN is heat-treated under the above conditions, (a) the sintered body 20
Al 3 Ti, which is an intermetallic compound, is formed on the surface layer of the TiN particles 21 in the inside.
Or a multiphase particle 22 is formed, or
(b) It is not always clear whether the TiN particles themselves change into Al 3 Ti particles 23, but in any case, a structure in which the Al 3 Ti phase is dispersed in the aluminum matrix is obtained. In both cases (a) and (b), unreacted TiN ultrafine particles 21 remain in the obtained composite material.
【００３１】AlとTiＮ粒子との反応の進行具合を適切に
制御し、Al3 Ti相の量（体積分率）、その相の大きさ等
を調節することで良好な物性を有する複合材とすること
ができる。By appropriately controlling the progress of the reaction between Al and TiN particles and adjusting the amount (volume fraction) of the Al 3 Ti phase, the size of the phase, etc., a composite material having good physical properties can be obtained. can do.
【００３２】上記組織を得るために、熱処理条件は上述
の通りとする。熱処理温度をあまり高いものとするか
（例えば７５０℃を超す温度とするか）、又は熱処理時
間を10時間を超すものとすれば、複合材の強度（圧縮強
度）及び硬度（ビッカース硬度）がかえって低下する。
これは、（イ)Al3 Tiが粒成長するためか、又は（ロ)Al3T
i相とアルミニウムマトリックスとの界面で整合性がと
れなくなる（たとえば両者の格子定数、熱膨張係数、弾
性率等の違いによる歪みの発生）ためであると思われ
る。In order to obtain the above structure, the heat treatment conditions are as described above. If the heat treatment temperature is set too high (for example, a temperature higher than 750 ° C.) or the heat treatment time is longer than 10 hours, the strength (compressive strength) and hardness (Vickers hardness) of the composite material will be changed. descend.
This may be due to (a) Al 3 Ti grain growth, or (b) Al 3 T
This is probably because the interface between the i-phase and the aluminum matrix becomes incompatible (for example, strain is generated due to the difference in the lattice constant, the thermal expansion coefficient, the elastic modulus, etc. of the two).
【００３３】一方、熱処理温度を金属アルミニウムの融
点未満とすると、Al3 Ti相がほとんど生成されない。ま
た、熱処理時間が１時間未満でもAl3 Ti相がほとんど生
成されない。なお、上述の熱処理条件の範囲内であれ
ば、Al3 Ti相の体積分率は３０〜４０％程度となる。On the other hand, if the heat treatment temperature is lower than the melting point of metallic aluminum, Al 3 Ti phase is hardly generated. Also, Al 3 Ti phase is hardly generated even if the heat treatment time is less than 1 hour. Incidentally, as long as it is within the range of heat treatment conditions mentioned above, the volume fraction of the Al 3 Ti phase is about 30-40%.
【００３４】複合材中のAl3 Tiの分率は、熱処理の温
度、時間を変化させる以外に、用いる超微粒子混合物中
のAlとTiＮの比率を変化させることでもコントロールす
ることができる。The fraction of Al 3 Ti in the composite material can be controlled by changing the ratio of Al and TiN in the ultrafine particle mixture used, in addition to changing the temperature and time of heat treatment.
【００３５】以上、TiＮ超微粒子とAl3 Ti相とがアルミ
ニウムマトリックス中に分散した複合材の製造について
説明したが、本発明はこれに限定されない。たとえば、
（イ)アルミニウムの超微粒子と窒化ジルコニウムの超微
粒子とを含有する混合物を用いて、Al（マトリックス）
−ZrAl3 相−AlＮ−ZrＮ超微粒子複合材、又はAl（マト
リックス）−ZrAl3 相−ZrＮ超微粒子複合材を製造する
ことができる。また、（ロ)アルミニウムの超微粒子と窒
化クロムの超微粒子とを含有する混合物を用いて、Al
（マトリックス）−CrAl4 相−AlＮ−Cr2 Ｎ超微粒子複
合材、又はAl（マトリックス）−CrAl4 相−Cr2 Ｎ超微
粒子複合材を製造することもできる。さらに、同様にし
て他の金属の窒化物（超微粒子）とその他の金属間化合
物相を分散した複合材を製造することもできる。The production of the composite material in which the TiN ultrafine particles and the Al 3 Ti phase are dispersed in the aluminum matrix has been described above, but the present invention is not limited to this. For example,
(A) Using a mixture containing ultrafine particles of aluminum and ultrafine particles of zirconium nitride, Al (matrix)
-ZrAl 3-phase -AlN-ZrN ultrafine composite, or Al can be produced (matrix) -ZrAl 3-phase -ZrN ultrafine composite. Further, using a mixture containing (b) ultrafine particles of aluminum and ultrafine particles of chromium nitride, Al
It is also possible to produce a (matrix) -CrAl 4 phase-AlN-Cr 2 N ultrafine particle composite material or an Al (matrix) -CrAl 4 phase-Cr 2 N ultrafine particle composite material. Further, a composite material in which a nitride of another metal (ultrafine particles) and another intermetallic compound phase are dispersed can be produced in the same manner.
【００３６】また、窒化物の超微粒子のみでなく、炭化
物、又はホウ化物の超微粒子を分散した複合材を製造す
ることもできる。たとえば、上述の窒素プラズマ−蒸発
金属反応法において、窒素ガスの代わりにＣＨ4 、Ｃ2
Ｈ4 等を用い、超微粒子の混合物中に超微粒子状の炭化
物を導入し、これを用いて複合材を製造すれば、超微粒
子状の炭化物が分散した複合材とすることができる。同
様に、反応ガスとしてＢ2 Ｈ4 、Ｂ4 Ｈ10等を用いれ
ば、超微粒子状のホウ化物を分散した複合材とすること
ができる。It is also possible to manufacture a composite material in which not only ultrafine particles of nitride but also ultrafine particles of carbide or boride are dispersed. For example, in the above-mentioned nitrogen plasma-evaporation metal reaction method, CH 4 , C 2 is used instead of nitrogen gas.
When H 4 or the like is used to introduce an ultrafine particle-like carbide into a mixture of ultrafine particles, and a composite material is produced using this, a composite material in which the ultrafine particle-like carbide is dispersed can be obtained. Similarly, if B 2 H 4 , B 4 H 10, etc. are used as the reaction gas, a composite material in which boride in the form of ultrafine particles is dispersed can be obtained.
【００３７】さらに、窒化物、炭化物、及びホウ化物の
超微粒子の２種以上を同時に含有する複合材としてもよ
い。Furthermore, a composite material containing at least two kinds of ultrafine particles of nitride, carbide and boride may be used.
【００３８】[0038]
【実施例】本発明を以下に示す具体的実施例によりさら
に詳細に説明する。実施例１ 金属Tiと金属Alとを秤量して混合し、アルゴンガス中で
アーク溶解して、Al40Ti60の組成を有する合金を作製し
た。EXAMPLES The present invention will be described in more detail with reference to the following specific examples. Example 1 Metal Ti and metal Al were weighed and mixed and arc-melted in an argon gas to prepare an alloy having a composition of Al 40 Ti 60 .
【００３９】この合金２０ｇを図１に示す装置１内のヒ
ース４に設置した。20 g of this alloy was placed on the heath 4 in the apparatus 1 shown in FIG.
【００４０】ガス注入口６の側のバルブ（図示せず）を
閉じ、排気口９からチャンバーを吸引し、上下チャンバ
ー２、３の圧力を１×10-4Torrとした。The valve (not shown) on the gas inlet 6 side was closed, the chamber was sucked through the exhaust port 9, and the pressure in the upper and lower chambers 2 and 3 was adjusted to 1 × 10 -4 Torr.
【００４１】次に、ガス注入口６から窒素ガスを上部チ
ャンバー２内に導入し、排気口９側のバルブ（図示せ
ず）を少々開けて下部チャンバー３の排気を再開した。
このとき、上部チャンバー２内の圧力が６００Torrに保
持されるように、ガス注入口６からの窒素ガスの注入量
及び排気口９からの排気量を調節した。Next, nitrogen gas was introduced into the upper chamber 2 through the gas inlet 6, the valve (not shown) on the exhaust port 9 side was slightly opened, and the exhaust of the lower chamber 3 was restarted.
At this time, the injection amount of nitrogen gas from the gas injection port 6 and the exhaust amount from the exhaust port 9 were adjusted so that the pressure in the upper chamber 2 was maintained at 600 Torr.
【００４２】上部チャンバー２内の窒素ガス圧が６００
Torrに保たれた状態で、２００Ａのアーク電流で合金を
加熱溶融した。ノズル11から超微粒子状の化合物が吹き
出され、ダイス８内に堆積物が得られた。The nitrogen gas pressure in the upper chamber 2 is 600
The alloy was heated and melted with an arc current of 200 A while being maintained at Torr. The ultrafine particle-like compound was blown out from the nozzle 11, and a deposit was obtained in the die 8.
【００４３】ダイス８内の堆積物の一部を取り出しＸ線
回折を行った。得られたチャートのピークの高さから、
堆積物はAlと、AlＮと、TiＮとが、ほぼ43％、50％、７
％（体積％）の割合で混合したものであることが推定さ
れた。A part of the deposit in the die 8 was taken out and subjected to X-ray diffraction. From the peak height of the obtained chart,
Al, AlN and TiN are almost 43%, 50%, 7
It was estimated that the mixture was a mixture of% (volume%).
【００４４】真空下で、ダイス８内の堆積物を１ＧPaで
圧粉成形し、ペレット状の成形体を作製した。Under vacuum, the deposit in the die 8 was powder compacted at 1 GPa to produce a pellet-shaped compact.
【００４５】この成形体を真空下（１×10-5Torr）、40
0 ℃、245 ＭPaの条件で60分間ホットプレスした。得ら
れた焼結体のＸ線回折を測定したところ、Al、AlＮ、Ti
Ｎに由来する大きなピークの他に、Al3 Tiに由来する小
さなピークが見られた。This molded body was placed under vacuum (1 × 10 −5 Torr) for 40
Hot pressing was performed for 60 minutes at 0 ° C. and 245 MPa. When the X-ray diffraction of the obtained sintered body was measured, it was found that Al, AlN, Ti
In addition to the large peak derived from N, a small peak derived from Al 3 Ti was observed.
【００４６】ホットプレス後、１×10-5Torrの真空下、
400 〜800 ℃の温度で１時間の熱処理を行った。得られ
た試料（複合材）について、再びＸ線回折を測定したと
ころ、Al、AlＮ、TiＮに由来するピークと、Al3 Tiに由
来するピークが見られた。After hot pressing, under a vacuum of 1 × 10 -5 Torr,
Heat treatment was performed at a temperature of 400 to 800 ° C. for 1 hour. When the X-ray diffraction was measured again for the obtained sample (composite material), peaks derived from Al, AlN, and TiN and peaks derived from Al 3 Ti were found.
【００４７】熱処理前のAl3 Tiのメインピーク（面１１
２及び面１０３に由来するピーク）の高さと、熱処理後
のこのメインピークの高さの比を求めた。結果を図４に
示す。Main peak of Al 3 Ti before heat treatment (plane 11
2) and the height of the main peak after the heat treatment were determined. FIG. 4 shows the results.
【００４８】また、各温度で熱処理して得られた試料
（複合材）のビッカース硬度及び圧縮強度を測定した。
なお、ビッカース硬度の測定はJIS Z 2251に準拠して調
べた。結果を図５に示す。The Vickers hardness and compressive strength of the sample (composite material) obtained by heat treatment at each temperature were measured.
The Vickers hardness was measured according to JIS Z 2251. Results are shown in FIG.
【００４９】[0049]
【発明の効果】以上に詳述したように、本発明の方法に
よれば、高強度、高硬度を有する粒子強化複合材を容易
に製造することができる。また、本発明の方法によれ
ば、窒化物超微粒子のみならず、炭化物又はホウ化物の
超微粒子を分散した複合材も製造することができる。As described in detail above, according to the method of the present invention, a particle-reinforced composite material having high strength and high hardness can be easily manufactured. Further, according to the method of the present invention, not only ultrafine particles of nitride but also composite material in which ultrafine particles of carbide or boride are dispersed can be produced.
【００５０】特に、窒素プラズマ−蒸発金属反応法によ
り、Al、AlＮ、TiＮの各超微粒子混合物を製造すれば、
予め、混合物中にTiＮ超微粒子を均一に分散させること
ができるので、複合材の製造過程においてAl3 Tiの偏析
は起こらない。In particular, if an ultrafine particle mixture of Al, AlN and TiN is produced by the nitrogen plasma-evaporation metal reaction method,
Since TiN ultrafine particles can be uniformly dispersed in the mixture in advance, segregation of Al 3 Ti does not occur in the manufacturing process of the composite material.
【００５１】本発明の方法による粒子強化複合材は、航
空機、自動車等の構造部材として用いることができる。The particle-reinforced composite material according to the method of the present invention can be used as a structural member for aircraft, automobiles and the like.
【図１】窒素プラズマ−蒸発金属反応法を実施すること
ができる装置の一例を示す模式的な断面図である。FIG. 1 is a schematic cross-sectional view showing an example of an apparatus capable of carrying out a nitrogen plasma-vapor metal reaction method.
【図２】Al−Ti合金の組成と、それを用いて超微粒子を
製造した超微粒子中の成分の体積分率との関係を示すグ
ラフである。FIG. 2 is a graph showing the relationship between the composition of an Al—Ti alloy and the volume fraction of components in ultrafine particles produced from the same.
【図３】Al−AlＮ−TiＮからなる焼結体を熱処理した場
合に想定される粒子の変化の様子を示す模式図である。FIG. 3 is a schematic view showing a state of change of particles assumed when a sintered body made of Al—AlN—TiN is heat-treated.
【図４】熱処理温度と、熱処理前後のAl3 TiのＸ線ピー
クの比との関係を示すグラフである。FIG. 4 is a graph showing a relationship between a heat treatment temperature and a ratio of X-ray peaks of Al 3 Ti before and after the heat treatment.
【図５】熱処理温度と得られた複合材のビッカース硬度
との関係、及び熱処理温度と得られた複合材の圧縮強度
との関係を示すグラフである。FIG. 5 is a graph showing the relationship between the heat treatment temperature and the Vickers hardness of the obtained composite material, and the relationship between the heat treatment temperature and the compressive strength of the obtained composite material.
１ 超微粒子製造装置 ２ 上部チャンバー ２ 下部チャンバー ４ ヒース ５ アーク電極 ６ ガス注入口 ８ ダイス ９ 排気口 10 管 11 ノズル 12 合金 1 Ultra Fine Particle Manufacturing Equipment 2 Upper Chamber 2 Lower Chamber 4 Heath 5 Arc Electrode 6 Gas Injection Port 8 Dice 9 Exhaust Port 10 Tube 11 Nozzle 12 Alloy
───────────────────────────────────────────────────── フロントページの続き (71)出願人 000215785 帝国ピストンリング株式会社 東京都中央区八重洲１丁目９番９号 (71)出願人 000005326 本田技研工業株式会社 東京都港区南青山二丁目１番１号 (72)発明者 野崎 勝敏 埼玉県和光市中央一丁目４番１号 株式会 社本田技術研究所内 ─────────────────────────────────────────────────── ─── Continued Front Page (71) Applicant 000215785 Teikoku Piston Ring Co., Ltd. 1-9-9 Yaesu, Chuo-ku, Tokyo (71) Applicant 000005326 Honda 1-1-1 Minami-Aoyama 2-chome, Minato-ku, Tokyo Issue (72) Inventor Katsutoshi Nozaki 1-4-1 Chuo 1-4-1 Wako-shi, Saitama Stock Company Honda R & D Co., Ltd.
Claims (3)
と、第二の金属の窒化物、炭化物、又はホウ化物のいず
れかからなる第二の超微粒子との混合物を製造し、(b)
前記混合物から成形体を作製し、(c) 前記成形体を前記
第一の金属の融点以上の温度で熱処理することにより、
前記第一の金属からなるマトリックス中に、前記第一の
金属と前記第二の金属とからなる金属間化合物相と、前
記第二の超微粒子とが分散してなる粒子強化複合材を製
造することを特徴とする方法。1. A mixture of (a) first ultrafine particles of a first metal and second ultrafine particles of a second metal nitride, carbide, or boride is produced. , (B)
A molded body is produced from the mixture, and (c) the molded body is heat-treated at a temperature equal to or higher than the melting point of the first metal,
A particle-reinforced composite material is produced in which an intermetallic compound phase composed of the first metal and the second metal and the second ultrafine particles are dispersed in a matrix composed of the first metal. A method characterized by the following.
一の超微粒子と第二の超微粒子との前記混合物を、前記
第一の金属と前記第二の金属とからなる合金に対して反
応ガス中でプラズマアーク放電を行うことにより作製す
ることを特徴とする方法。2. The method according to claim 1, wherein the mixture of the first ultrafine particles and the second ultrafine particles is added to an alloy composed of the first metal and the second metal. A method characterized by being produced by performing plasma arc discharge in a reaction gas.
一及び第二の金属としてそれぞれアルミニウム及びチタ
ンを用いるとともに前記反応ガスとして窒素を用い、プ
ラズマアーク放電を行ってAlとTiＮとを含有する超微粒
子混合物を製造し、前記混合物から、金属アルミニウム
のマトリックス中に、Al3 Ti相と窒化チタン超微粒子と
が分散した粒子強化複合材とすることを特徴とする方
法。3. The method according to claim 2, wherein aluminum and titanium are used as the first and second metals, respectively, and nitrogen is used as the reaction gas, and plasma arc discharge is performed to contain Al and TiN. A method of producing a particle-reinforced composite material, in which an Al 3 Ti phase and ultrafine titanium nitride particles are dispersed in a matrix of metallic aluminum from the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4257293A JP2863675B2 (en) | 1992-09-01 | 1992-09-01 | Manufacturing method of particle reinforced composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4257293A JP2863675B2 (en) | 1992-09-01 | 1992-09-01 | Manufacturing method of particle reinforced composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07207381A true JPH07207381A (en) | 1995-08-08 |
| JP2863675B2 JP2863675B2 (en) | 1999-03-03 |
Family
ID=17304361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4257293A Expired - Lifetime JP2863675B2 (en) | 1992-09-01 | 1992-09-01 | Manufacturing method of particle reinforced composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2863675B2 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007533861A (en) * | 2004-04-19 | 2007-11-22 | エスディーシー マテリアルズ リミテッド ライアビリティ カンパニー | High-throughput material discovery method by vapor phase synthesis |
| JP2008532772A (en) * | 2005-03-16 | 2008-08-21 | サントル ド ルシェルシュ メタリュルジク アエスベエル−セントラム ヴォール リサーチ イン デ メタルージー フェーゼットヴェー | Method for continuous casting of metals with improved mechanical strength and products obtained by this method |
| US8969237B2 (en) | 2011-08-19 | 2015-03-03 | SDCmaterials, Inc. | Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions |
| US9023754B2 (en) | 2005-04-19 | 2015-05-05 | SDCmaterials, Inc. | Nano-skeletal catalyst |
| US9089840B2 (en) | 2007-10-15 | 2015-07-28 | SDCmaterials, Inc. | Method and system for forming plug and play oxide catalysts |
| US9126191B2 (en) | 2009-12-15 | 2015-09-08 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9149797B2 (en) | 2009-12-15 | 2015-10-06 | SDCmaterials, Inc. | Catalyst production method and system |
| US9156025B2 (en) | 2012-11-21 | 2015-10-13 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9216406B2 (en) | 2011-02-23 | 2015-12-22 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PtPd catalysts |
| US9332636B2 (en) | 2009-12-15 | 2016-05-03 | SDCmaterials, Inc. | Sandwich of impact resistant material |
| US9427732B2 (en) | 2013-10-22 | 2016-08-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9517448B2 (en) | 2013-10-22 | 2016-12-13 | SDCmaterials, Inc. | Compositions of lean NOx trap (LNT) systems and methods of making and using same |
| US9522388B2 (en) | 2009-12-15 | 2016-12-20 | SDCmaterials, Inc. | Pinning and affixing nano-active material |
| US9586179B2 (en) | 2013-07-25 | 2017-03-07 | SDCmaterials, Inc. | Washcoats and coated substrates for catalytic converters and methods of making and using same |
| US9687811B2 (en) | 2014-03-21 | 2017-06-27 | SDCmaterials, Inc. | Compositions for passive NOx adsorption (PNA) systems and methods of making and using same |
-
1992
- 1992-09-01 JP JP4257293A patent/JP2863675B2/en not_active Expired - Lifetime
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007533861A (en) * | 2004-04-19 | 2007-11-22 | エスディーシー マテリアルズ リミテッド ライアビリティ カンパニー | High-throughput material discovery method by vapor phase synthesis |
| JP2008532772A (en) * | 2005-03-16 | 2008-08-21 | サントル ド ルシェルシュ メタリュルジク アエスベエル−セントラム ヴォール リサーチ イン デ メタルージー フェーゼットヴェー | Method for continuous casting of metals with improved mechanical strength and products obtained by this method |
| US9132404B2 (en) | 2005-04-19 | 2015-09-15 | SDCmaterials, Inc. | Gas delivery system with constant overpressure relative to ambient to system with varying vacuum suction |
| US9023754B2 (en) | 2005-04-19 | 2015-05-05 | SDCmaterials, Inc. | Nano-skeletal catalyst |
| US9719727B2 (en) | 2005-04-19 | 2017-08-01 | SDCmaterials, Inc. | Fluid recirculation system for use in vapor phase particle production system |
| US9180423B2 (en) | 2005-04-19 | 2015-11-10 | SDCmaterials, Inc. | Highly turbulent quench chamber |
| US9216398B2 (en) | 2005-04-19 | 2015-12-22 | SDCmaterials, Inc. | Method and apparatus for making uniform and ultrasmall nanoparticles |
| US9599405B2 (en) | 2005-04-19 | 2017-03-21 | SDCmaterials, Inc. | Highly turbulent quench chamber |
| US9089840B2 (en) | 2007-10-15 | 2015-07-28 | SDCmaterials, Inc. | Method and system for forming plug and play oxide catalysts |
| US9592492B2 (en) | 2007-10-15 | 2017-03-14 | SDCmaterials, Inc. | Method and system for forming plug and play oxide catalysts |
| US9597662B2 (en) | 2007-10-15 | 2017-03-21 | SDCmaterials, Inc. | Method and system for forming plug and play metal compound catalysts |
| US9737878B2 (en) | 2007-10-15 | 2017-08-22 | SDCmaterials, Inc. | Method and system for forming plug and play metal catalysts |
| US9186663B2 (en) | 2007-10-15 | 2015-11-17 | SDCmaterials, Inc. | Method and system for forming plug and play metal compound catalysts |
| US9302260B2 (en) | 2007-10-15 | 2016-04-05 | SDCmaterials, Inc. | Method and system for forming plug and play metal catalysts |
| US9308524B2 (en) | 2009-12-15 | 2016-04-12 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9149797B2 (en) | 2009-12-15 | 2015-10-06 | SDCmaterials, Inc. | Catalyst production method and system |
| US9126191B2 (en) | 2009-12-15 | 2015-09-08 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9332636B2 (en) | 2009-12-15 | 2016-05-03 | SDCmaterials, Inc. | Sandwich of impact resistant material |
| US9533289B2 (en) | 2009-12-15 | 2017-01-03 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9522388B2 (en) | 2009-12-15 | 2016-12-20 | SDCmaterials, Inc. | Pinning and affixing nano-active material |
| US9433938B2 (en) | 2011-02-23 | 2016-09-06 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PTPD catalysts |
| US9216406B2 (en) | 2011-02-23 | 2015-12-22 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PtPd catalysts |
| US9498751B2 (en) | 2011-08-19 | 2016-11-22 | SDCmaterials, Inc. | Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions |
| US8969237B2 (en) | 2011-08-19 | 2015-03-03 | SDCmaterials, Inc. | Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions |
| US9156025B2 (en) | 2012-11-21 | 2015-10-13 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9533299B2 (en) | 2012-11-21 | 2017-01-03 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9586179B2 (en) | 2013-07-25 | 2017-03-07 | SDCmaterials, Inc. | Washcoats and coated substrates for catalytic converters and methods of making and using same |
| US9427732B2 (en) | 2013-10-22 | 2016-08-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| US9566568B2 (en) | 2013-10-22 | 2017-02-14 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| US9517448B2 (en) | 2013-10-22 | 2016-12-13 | SDCmaterials, Inc. | Compositions of lean NOx trap (LNT) systems and methods of making and using same |
| US9950316B2 (en) | 2013-10-22 | 2018-04-24 | Umicore Ag & Co. Kg | Catalyst design for heavy-duty diesel combustion engines |
| US9687811B2 (en) | 2014-03-21 | 2017-06-27 | SDCmaterials, Inc. | Compositions for passive NOx adsorption (PNA) systems and methods of making and using same |
| US10086356B2 (en) | 2014-03-21 | 2018-10-02 | Umicore Ag & Co. Kg | Compositions for passive NOx adsorption (PNA) systems and methods of making and using same |
| US10413880B2 (en) | 2014-03-21 | 2019-09-17 | Umicore Ag & Co. Kg | Compositions for passive NOx adsorption (PNA) systems and methods of making and using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2863675B2 (en) | 1999-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH07207381A (en) | Production of particle reinforced composite material | |
| US5059490A (en) | Metal-ceramic composites containing complex ceramic whiskers | |
| EP0345045B1 (en) | Method of making tungsten-titanium sputtering targets | |
| US5348806A (en) | Cermet alloy and process for its production | |
| US5912399A (en) | Chemical synthesis of refractory metal based composite powders | |
| US5640666A (en) | Composite silicide/silicon carbide mechanical alloy | |
| JPS58171502A (en) | Pulverized composite powder of ceramic and metal | |
| EP1715070B1 (en) | Method of producing titanium composite parts by means of casting | |
| US4915902A (en) | Complex ceramic whisker formation in metal-ceramic composites | |
| US6187260B1 (en) | Aluminum metal matrix composite materials reinforced by intermetallic compounds and alumina whiskers | |
| US5534353A (en) | Composite sintered material having fine particles of hard compound dispersed in grains of titanium or titanium alloy matrix | |
| JPH0610281B2 (en) | Ceramic-metal composite fine powder | |
| EP0250163B1 (en) | A method for the preparation of an alloy of nickel and titanium | |
| JP2004346368A (en) | Method for manufacturing composite material, and composite material | |
| JPH08176695A (en) | Production of titanium nitride sinter | |
| JP3793813B2 (en) | High strength titanium alloy and method for producing the same | |
| JPH1112758A (en) | Metallic parts coated with cermet sintered compact, and their production | |
| JPS63199843A (en) | Composite molded body of molybdenum or its alloy and zirconia and its production | |
| JP2000144301A (en) | Tungsten carbide sintered body and its production | |
| JPH06100969A (en) | Production of ti-al intermetallic compound sintered body | |
| Levi et al. | Consolidation of rapidly solidified intermetallic powders using the Ceracon® process | |
| JPH08260129A (en) | Cubic boron nitride composite cermet tool and its production | |
| JPH05302134A (en) | Sintered hard alloy and its manufacture | |
| JPH0633165A (en) | Manufacture of sintered titanium alloy | |
| JPH06228677A (en) | Combined sintered alloy excellent in corrosion and wear resistance and production thereof |