JPH0492857A - Composite sintered material having high abrasion resistance - Google Patents
Composite sintered material having high abrasion resistanceInfo
- Publication number
- JPH0492857A JPH0492857A JP2210600A JP21060090A JPH0492857A JP H0492857 A JPH0492857 A JP H0492857A JP 2210600 A JP2210600 A JP 2210600A JP 21060090 A JP21060090 A JP 21060090A JP H0492857 A JPH0492857 A JP H0492857A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- sintered body
- weight
- composite sintered
- metal oxide
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title abstract description 15
- 238000005299 abrasion Methods 0.000 title abstract description 5
- 239000006104 solid solution Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 25
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 25
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 25
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 6
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical group [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims description 4
- 229910003470 tongbaite Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 239000003381 stabilizer Substances 0.000 description 15
- 238000005520 cutting process Methods 0.000 description 14
- 230000007423 decrease Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000003466 welding Methods 0.000 description 8
- 239000007858 starting material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- IHNDUGMUECOVKK-UHFFFAOYSA-N aluminum chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[O-2].[Al+3] IHNDUGMUECOVKK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐摩耗性、耐溶着性、潤滑性１強度、靭性及
び面精度にすぐれる酸化物系複合焼結体に関し、具体的
には、旋削工具、フライス工具に代表される切削工具又
は製缶工具、スリッターに代表される耐摩耗工具に適す
る高耐摩耗性複合焼結体に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an oxide-based composite sintered body having excellent wear resistance, welding resistance, lubricity, strength, toughness, and surface precision. The present invention relates to a highly wear-resistant composite sintered body suitable for cutting tools such as turning tools and milling tools, or can-making tools, and wear-resistant tools such as slitters.
（従来の技術）
従来、切削工具又は耐摩耗工具として使用されている酸
化物系複合焼結体としては、 ＡＡ 、０３−ＭｇＯ系
焼結体とＺｒ０ｚ−Ｙａｋｓ系焼結体に大別できる。こ
の内５部者は、耐摩耗性にすぐれるものの靭性が極端に
低く、欠損しやすいこと、後習は。(Prior Art) Oxide-based composite sintered bodies conventionally used as cutting tools or wear-resistant tools can be broadly classified into AA, 03-MgO-based sintered bodies and Zr0z-Yaks-based sintered bodies. Of these, five types have excellent wear resistance, but their toughness is extremely low and they are easily damaged, as you will learn later.
相変態に伴う体積膨張によりクラック伝播を阻止する作
用が働き、高破壊靭性値及び高強度になったけれども、
低硬度であること、特に高温時での硬度低下が著しく耐
摩耗性に劣るという問題がある。これらの問題を解決し
ようとしたものが多数提案されており、この内、＾ｔ２
！０ｓ−ＺｒＯｘ−Ｃｒａｂｓ三成分を主体にした焼
結体の代表的なものに特開平１−２９０５５７号公報が
ある。Although the volume expansion associated with phase transformation acts to prevent crack propagation, resulting in high fracture toughness and high strength,
There is a problem that the hardness is low, and the hardness decreases significantly especially at high temperatures, resulting in poor wear resistance. Many methods have been proposed to solve these problems, among which ^t2
! JP-A-1-290557 is a typical example of a sintered body mainly composed of the three components 0s-ZrOx-Crabs.
（発明が解決しようとする課題）
特開平１−２９０５５７号公報には、１〜５モル％の安
定化剤を含むＺｒＯ□６０〜９５重量％と１〜２０重量
％のＣｒａｂｓを固溶するＡβ２０．固溶体とからなる
複合焼結体が開示されている。(Problems to be Solved by the Invention) JP-A-1-290557 describes Aβ20 in which 60 to 95% by weight of ZrO containing 1 to 5 mol% of a stabilizer and 1 to 20% by weight of Crabs are dissolved. ．． A composite sintered body comprising a solid solution is disclosed.
この同公報に開示の複合焼結体は、高強度及び高靭性を
達成させたすぐれた焼結体であるけれども、高温での耐
溶着性、耐摩耗性が劣ること、潤滑性が低いこと及び面
精度が劣ることから耐摩耗工具としての用途が限定され
ること、並びに切削工具としての実用化が困難であると
いう問題がある。Although the composite sintered body disclosed in this publication is an excellent sintered body that has achieved high strength and high toughness, it has poor welding resistance and wear resistance at high temperatures, low lubricity, and There are problems in that its use as a wear-resistant tool is limited due to poor surface precision, and it is difficult to put it into practical use as a cutting tool.
本発明は、上述のような問題点を解決したもので、具体
的には、酸化アルミニウムと酸化クロムと安定化剤を含
んだ酸化ジルコニウムとをバランスよく調整して、それ
ぞれの特性を最大限に発揮させることに成功した切削工
具又は耐摩耗工具としてすぐれた高耐摩耗性複合焼結体
の提供を目的とするものである。The present invention solves the above-mentioned problems. Specifically, aluminum oxide, chromium oxide, and zirconium oxide containing a stabilizer are adjusted in a well-balanced manner to maximize their respective properties. The object of the present invention is to provide a highly wear-resistant composite sintered body that can be successfully used as a cutting tool or a wear-resistant tool.
（課題を解決するための手段）
本発明者らは、鋼、鋳物などの被加工材を切削加工する
場合、又はＳＵＳ材、 Ｃｕ合金、Ａ℃金合金どの被加
工材を塑性加工もしくは切断加工する場合に、被加工材
が工具の加工面に溶着あるいは付着し、これが原因とな
って工具の加工面の摩耗が急激に進行し、被加工材の被
加工面の荒れが激しくなるということに対する検討を行
っていた所、
第１に、酸化クロムを含む焼結体は、被加工材である金
属と溶着し難く、摩擦係数が低いこと及び研摩加工を行
ったとき、焼結体の被加工面の精度が高くなること、こ
の結果、工具として使用したときに被加工材の付着が著
しく減少するという知見を得たものである。(Means for Solving the Problems) When cutting workpieces such as steel and castings, or plastic working or cutting workpieces such as SUS materials, Cu alloys, and A℃ gold alloys, the present inventors When the workpiece is welded or attached to the machined surface of the tool, this causes rapid wear on the machined surface of the tool, and the roughness of the machined surface of the workpiece becomes severe. First, a sintered body containing chromium oxide has a low coefficient of friction and is difficult to weld to the metal being processed, and when polished, the sintered body is difficult to weld to the metal being processed. It was discovered that the surface accuracy is increased, and as a result, the adhesion of workpiece materials when used as a tool is significantly reduced.
第２に、苛酷な切削工具として実用可能な耐摩耗性、靭
性な保持させ、かつ上述の酸化クロムの効果を最大限に
発揮させるためには、酸化クロムと固溶しやすい、主と
して耐摩耗性の向上に効果のある酸化アルミニウムと、
主として靭性の向上に効果のある酸化ジルコニウムと、
酸化クロムとの三成分の組成の調整により、達成するこ
とができるという知見を得たものである。Secondly, in order to maintain wear resistance and toughness that can be used as a practical cutting tool and to maximize the effects of chromium oxide mentioned above, it is necessary to maintain wear resistance and toughness that are easy to form a solid solution with chromium oxide. Aluminum oxide, which is effective in improving
Zirconium oxide, which is mainly effective in improving toughness,
We have found that this can be achieved by adjusting the composition of the three components with chromium oxide.
この第１と第２の知見に基づいて、本発明を完成するに
至ったものである。Based on these first and second findings, we have completed the present invention.
すなわち、本発明の高耐摩耗性複合焼結体は。That is, the highly wear-resistant composite sintered body of the present invention is.
ＭｇＯ，Ｃａｂ、希土類酸化物及びこれらの相互固溶体
の中の少なくとも１種を１〜５モル％含有する酸化ジル
コニウム１０〜８５重量％と酸化クロム１０〜７２重量
％と酸化アルミニウム５〜８０重量％とでなる金属酸化
物相と不可避不純物とからなることを特徴とするもので
ある。10 to 85% by weight of zirconium oxide, 10 to 72% by weight of chromium oxide, and 5 to 80% by weight of aluminum oxide, containing 1 to 5 mol% of at least one of MgO, Cab, rare earth oxides, and mutual solid solutions thereof. It is characterized by consisting of a metal oxide phase and inevitable impurities.
本発明の高耐摩耗性複合焼結体における酸化ジルコニウ
ムは、１部又は全部が正方晶の結晶構造からなっている
と、−層、高靭性な焼結体を得ることができるので好ま
しく、具体的には、単斜晶と正方晶、又は全部が正方晶
、もしくは正方晶と立方晶、あるいは単斜晶と正方晶と
立方晶とからなるものである。この酸化ジルコニウム中
に含有する安定化剤は、具体的には、ＭｇＯ，Ｃａｎ、
又はＳｃ、 Ｙ、 ランタノイドの酸化物でなる希土
類酸化物及びこれらの相互固溶体の中の少なくとも１種
からなるものである。It is preferable that the zirconium oxide in the highly wear-resistant composite sintered body of the present invention has a tetragonal crystal structure, in part or in its entirety, since this makes it possible to obtain a highly tough sintered body. Specifically, it is composed of monoclinic and tetragonal crystals, entirely tetragonal crystals, tetragonal crystals and cubic crystals, or monoclinic crystals, tetragonal crystals, and cubic crystals. Specifically, the stabilizer contained in this zirconium oxide includes MgO, Can,
Or, it is made of at least one of rare earth oxides such as oxides of Sc, Y, and lanthanoids, and mutual solid solutions of these.
この酸化ジルコニウムの中の安定化剤が１モル％未満に
なると、焼結体の中に単斜晶酸化ジルコニウムの量が多
くなること、逆に安定化剤が５モル％を超えて多くなる
と焼結体の中に立方晶酸化ジルコニウムの置が多くなる
ことにより、いずれも切削工具としての耐欠損性、耐摩
耗工具としての強度及び耐摩耗性の低下となる。このた
めに。If the stabilizer content in the zirconium oxide is less than 1 mol%, the amount of monoclinic zirconium oxide in the sintered body will increase, and conversely, if the stabilizer content exceeds 5 mol%, the sintered body will be sintered. As the amount of cubic zirconium oxide increases in the compact, the fracture resistance as a cutting tool and the strength and wear resistance as a wear-resistant tool decrease. For this.
酸化ジルコニウム中の安定化剤を１〜５モル％と定めた
ものである。この安定化剤を含有した酸化ジルコニウム
が焼結体全体の１（Ｉｆｆ％未満になると、酸化ジルコ
ニウムの正方晶から単斜晶への相変態による靭性改善の
効果が少なくて、強度低下が著しくなること、逆に８５
重量％を超えて多くなると、相対的に酸化アルミニウム
及び酸化クロムの含有量が減少して、耐摩耗性、潤滑性
及び耐溶着性が劣ることになる。このために、安定化剤
を含有した酸化ジルコニウムは、焼結体全体の１０〜８
５重量％、好ましくは１０〜７０重量％である。The amount of stabilizer in zirconium oxide is determined to be 1 to 5 mol%. If the amount of zirconium oxide containing this stabilizer is less than 1 (Iff%) of the entire sintered body, the effect of improving toughness due to the phase transformation of zirconium oxide from tetragonal to monoclinic will be small, resulting in a significant decrease in strength. On the contrary, 85
When the amount exceeds % by weight, the content of aluminum oxide and chromium oxide decreases relatively, resulting in poor wear resistance, lubricity, and welding resistance. For this purpose, zirconium oxide containing a stabilizer is added to 10 to 8
5% by weight, preferably 10-70% by weight.
この安定化剤を含有した酸化ジルコニウムの他に、本発
明の高耐摩耗性複合焼結体を構成している酸化クロムと
酸化アルミニウムは、１部又は全部が相互固溶体になっ
ていると、−層耐摩耗性。In addition to the stabilizer-containing zirconium oxide, chromium oxide and aluminum oxide, which constitute the highly wear-resistant composite sintered body of the present invention, are partially or completely in a solid solution with each other. Layer abrasion resistance.
潤滑性、耐溶着性及び緻密性のすぐれた焼結体を得るこ
とができるので好ましく、具体的には、酸化クロムと酸
化クロム−酸化アルミニウムの固溶体、又は酸化クロム
−酸化アルミニウムの固溶体のみ、もしくは酸化クロム
−酸化アルミニウムの固溶体と酸化アルミニウム、ある
いは酸化クロムと酸化アルミニウムと酸化クロム−酸化
アルミニウムの固溶体からなるものである。It is preferable because a sintered body with excellent lubricity, welding resistance, and density can be obtained, and specifically, a solid solution of chromium oxide and chromium oxide-aluminum oxide, or only a solid solution of chromium oxide-aluminum oxide, or It consists of a solid solution of chromium oxide-aluminum oxide and aluminum oxide, or a solid solution of chromium oxide, aluminum oxide, and chromium oxide-aluminum oxide.
これらの内、酸化クロムが焼結体全体の１０重量％未満
になると、耐溶着性及び潤滑性が低下し、その結果耐欠
損性、耐摩耗性が低下し、逆に７２重量％を超えて多く
なると、相対的に酸化ジルコニウム及び酸化アルミニウ
ムの含有量が減少して。Among these, when chromium oxide is less than 10% by weight of the entire sintered body, the welding resistance and lubricity decrease, resulting in a decrease in chipping resistance and wear resistance; When it increases, the content of zirconium oxide and aluminum oxide decreases relatively.
耐摩耗性及び靭性の低下となる。このために、焼結体中
の酸化クロムの量は、１０〜７２重量％、特に好ましく
は１５〜４５重量％である。This results in a decrease in wear resistance and toughness. For this purpose, the amount of chromium oxide in the sintered body is between 10 and 72% by weight, particularly preferably between 15 and 45% by weight.
一方、酸化アルミニウムが焼結体全体の５重量％未渦に
なると、耐摩耗性の低下が著しく、逆に、８０重量％を
超えて多くなると、靭性及び耐溶着性が低下して欠損し
やすくなる。このために、焼結体中の酸化アルミニウム
の量は、５〜８０重量％、特に好ましくは５〜６０重量
％である。On the other hand, if aluminum oxide accounts for 5% by weight of the entire sintered body, the wear resistance decreases significantly, and conversely, if it exceeds 80% by weight, the toughness and welding resistance decreases, making chipping more likely. Become. For this purpose, the amount of aluminum oxide in the sintered body is between 5 and 80% by weight, particularly preferably between 5 and 60% by weight.
この本発明の高耐摩耗性複合焼結体は、安定化剤の含有
した酸化ジルコニウムと酸化クロムと酸化アルミニウム
との金属酸化物相の含有率により、最適効果が異なるも
ので、特に、切削工具として用いる場合には、特に安定
化剤の含有した酸化ジルコニウム２０〜５０重量％と酸
化クロム１５〜４０重量％と酸化アルミニウム２５〜５
５重量％とでなる焼結体が好ましく、耐摩耗工具として
用いる場合には、特に安定化剤の含有した酸化ジルコニ
ウム５０〜７０重量％と酸化クロム１５〜３５重量％と
酸化アルミニウム９〜２５重量％とでなる焼結体が好ま
しいものである。The optimum effect of the highly wear-resistant composite sintered body of the present invention differs depending on the content of the metal oxide phase of zirconium oxide, chromium oxide, and aluminum oxide contained in the stabilizer. In particular, when used as a stabilizer, 20 to 50% by weight of zirconium oxide, 15 to 40% by weight of chromium oxide, and 25 to 5% by weight of aluminum oxide are used as stabilizers.
A sintered body containing 5% by weight of zirconium oxide, 50 to 70% by weight of zirconium oxide, 15 to 35% by weight of chromium oxide, and 9 to 25% by weight of aluminum oxide, especially when used as a wear-resistant tool, is preferred. % is preferred.
本発明の高耐摩耗性複合焼結体における金属酸化物相は
、金属酸化物相の１０重量％以下をＣｒ。In the metal oxide phase in the highly wear-resistant composite sintered body of the present invention, 10% by weight or less of the metal oxide phase is Cr.
Ｃｏ、 Ｎｉ、 Ｆｅ及びこれらの相互合金の中の少な
くとも１種の金属相で置換すると、焼結体の強度及び靭
性な高める効果があることから、強度及び靭性を重要視
する耐摩耗工具に対しては好ましいことである。この場
合の金属相は、Ｃｒ−Ｎｉ合金、 Ｃｒ−Ｎｉ−Ｃｏ合
金、 Ｃｒ−Ｎｉ−Ｆｅ合金、 Ｃｒ−Ｎｉ−Ｃｏ−Ｆ
ｅ合金のように、ＣｒとＮｉの含有した合金が特に好ま
しく。Substitution with at least one metal phase among Co, Ni, Fe, and their mutual alloys has the effect of increasing the strength and toughness of the sintered body, so it is suitable for wear-resistant tools where strength and toughness are important. This is a good thing. The metal phase in this case is Cr-Ni alloy, Cr-Ni-Co alloy, Cr-Ni-Fe alloy, Cr-Ni-Co-F
An alloy containing Cr and Ni, such as e-alloy, is particularly preferred.
これらの内、 Ｃｒｌの多い合金の場合は、耐熱性及び
耐酸化性にすぐれる。Among these, alloys containing a large amount of Crl have excellent heat resistance and oxidation resistance.
また、この金属酸化物相は、その３０重量％以下を炭ク
ロムで置換することも焼結体の強度及び靭性を高める効
果がある。Furthermore, replacing 30% by weight or less of this metal oxide phase with chromium carbonate has the effect of increasing the strength and toughness of the sintered body.
本発明の高耐摩耗性複合焼結体は、従来から行われてい
る粉末冶金の製造方法を応用することにより作製するこ
とができるけれども、下記の方法で行うと緻密な焼結体
が得られやすく好ましいことである。Although the highly wear-resistant composite sintered body of the present invention can be produced by applying a conventional powder metallurgy manufacturing method, a dense sintered body cannot be obtained by the method described below. This is easy and desirable.
まず、出発物質の内、安定化剤と酸化ジルコニウムは、
それぞれ単独で用いてもよいが、安定化剤を酸化ジルコ
ニウム中に含有した固溶体の状態で用いると焼結体の靭
性を高める効果があるので好ましいことである。また、
出発物質としての酸化アルミニウムと酸化クロムも焼結
時に全率固溶するので、それぞれを単独で用いてもよい
が、予め固溶体化処理して用いると、焼結時での粒成長
の抑制と、焼結体の強度及び耐摩耗性を高める効果があ
るので好ましいことである。First, among the starting materials, the stabilizer and zirconium oxide are
Although each may be used alone, it is preferable to use the stabilizer in the form of a solid solution containing it in zirconium oxide, since this has the effect of increasing the toughness of the sintered body. Also,
Aluminum oxide and chromium oxide as starting materials also completely dissolve in solid solution during sintering, so each may be used alone, but if used after being treated as a solid solution in advance, grain growth during sintering can be suppressed. This is preferable since it has the effect of increasing the strength and wear resistance of the sintered body.
金属酸化物相を金属相で置換してなる焼結体を作製する
場合は、金属相を形成するための金属の粉末の他に、金
属相を形成するための金属の酸化物とその還元当量の炭
素とを出発物質として用いる方法、又は、例えばＣＨ，
、ＣＯガス含有の浸炭性雰囲気中で焼結して金属相を形
成するための金属の酸化物から金属相を析出させること
もできる。When producing a sintered body in which the metal oxide phase is replaced with a metal phase, in addition to the metal powder to form the metal phase, the metal oxide and its reduction equivalent to form the metal phase are used. as a starting material, or for example CH,
The metal phase can also be precipitated from an oxide of the metal for sintering in a carburizing atmosphere containing , CO gas to form the metal phase.
特に、金属相を形成させる場合、その金属の酸化物を出
発物質として用いると、金属相が微細均に分散すること
、焼結体の強度及び耐摩耗性がすぐれることから好まし
いことである。In particular, when forming a metal phase, it is preferable to use an oxide of the metal as a starting material because the metal phase is finely and uniformly dispersed and the sintered body has excellent strength and wear resistance.
また、金属酸化物相を炭化クロムで置換してなる焼結体
を作製する場合は、Ｃｒ５Ｃｚ、 Ｃｒ７ｃｓ、 Ｃｒ
と炭素の混合物、又は酸化クロムと炭素の混合物を出発
物質として用いることができる。これらの内、酸化クロ
ムと炭素の混合物を出発物質として用いた場合、炭化ク
ロムの生成反応以外に金属クロムの生成と、酸化クロム
−酸化アルミニウムの固溶反応をも伴う、一種の反応焼
結が起るので好ましいことである。In addition, when producing a sintered body in which the metal oxide phase is replaced with chromium carbide, Cr5Cz, Cr7cs, Cr
Mixtures of chromium oxide and carbon or chromium oxide and carbon can be used as starting materials. Among these, when a mixture of chromium oxide and carbon is used as a starting material, a type of reactive sintering occurs that involves the production of metallic chromium and the solid solution reaction of chromium oxide and aluminum oxide in addition to the reaction that produces chromium carbide. This is a good thing because it happens.
これらの出発物質を混合する場合は、例えば、ポリウレ
タン内張したステンレス製混合容器を用いて、メタノー
ルなどの有機溶媒中でボールミル混合粉砕すると、不純
物の混入を防止しやすいことから好ましい方法である。When mixing these starting materials, for example, using a stainless steel mixing container lined with polyurethane, ball milling and pulverizing in an organic solvent such as methanol is a preferred method because it is easy to prevent contamination of impurities.
このようにして得た混合粉末をホットプレス焼結する場
合は、窒化ホウ素（ｈＢＮ）粉末を塗布したカーボンモ
ールドに混合粉末を充填して、Ｎ、又は不活性ガス中で
、温度１３００〜１５００℃、圧力的２００ｋｇｆ／ｃ
ｍ”の条件で行うことができる。When hot-press sintering the mixed powder obtained in this way, the mixed powder is filled into a carbon mold coated with boron nitride (hBN) powder, and heated at a temperature of 1300 to 1500°C in N or inert gas. , pressure 200kgf/c
It can be carried out under the conditions of "m".
また、常圧焼結する場合は、混合粉末に成形用バインダ
ーを添加して、例えば］ ｔｏｎ／ｃｍ”以上の圧力で
モールド成形又は静水圧成形により成形体とし、成形体
中の成形用バインダーを除去後。In addition, in the case of pressureless sintering, a molding binder is added to the mixed powder, and a molded body is formed by molding or isostatic pressing at a pressure of, for example, 1 ton/cm" or higher, and the molding binder in the molded body is removed. After removal.
１４００〜１６００℃の温度で行うことができる。It can be carried out at a temperature of 1400-1600°C.
さらに、真空、ガス減圧又はガス加圧の雰囲気中で焼結
する場合１例えば、金属相もしくは炭化クロムの含有し
た焼結体を得るには、非酸化性あるいは浸炭性雰囲気に
する必要がある。特に、金属相としてＣｒを約０１〜３
重量％分散させた焼結体を得る場合には、酸化ジルコニ
ウムと酸化アルミニウムと酸化クロムとの混合粉末をカ
ーボンモールド中でホットプレス焼結、又はカーボンヒ
タ炉で真空もしくは減圧焼結するだけで容易に得ること
ができる。Furthermore, in the case of sintering in a vacuum, gas reduced pressure, or gas pressurized atmosphere, for example, in order to obtain a sintered body containing a metal phase or chromium carbide, it is necessary to use a non-oxidizing or carburizing atmosphere. In particular, Cr as the metal phase is about 01 to 3
In order to obtain a sintered body in which the weight percent is dispersed, it is easy to do so simply by hot-press sintering a mixed powder of zirconium oxide, aluminum oxide, and chromium oxide in a carbon mold, or by sintering it in vacuum or under reduced pressure in a carbon heater furnace. Obtainable.
このようにして得た焼結体を、例えばＡｒ又はＮ。The sintered body thus obtained is heated using, for example, Ar or N.
中、Ｉ ０００〜２０００ａｔｍの圧力、１２００〜１
５００℃の温度で熱間静水圧加圧処理（ＨＩＰ処理）を
行って、焼結体の強度及び耐摩耗性の改善を行うことも
好ましいことである。Medium, pressure of I 000-2000 atm, 1200-1
It is also preferable to perform a hot isostatic pressing treatment (HIP treatment) at a temperature of 500° C. to improve the strength and wear resistance of the sintered body.
（作用）
本発明の高耐摩耗性複合焼結体は、１部又は全部が固溶
体になった酸化アルミニウムと酸化クロムとの相の中に
安定化剤を含有した酸化ジルコニウムが均一に分布して
緻密な焼結体を形成し、この焼結体中の安定化酸化ジル
コニウムが主として強度及び靭性を高める作用をし、酸
化アルミニウムと酸化クロムとの相が耐摩耗性、耐溶着
性。(Function) The highly wear-resistant composite sintered body of the present invention has zirconium oxide containing a stabilizer uniformly distributed in a phase of aluminum oxide and chromium oxide, part or all of which is a solid solution. It forms a dense sintered body, and the stabilized zirconium oxide in this sintered body mainly works to increase strength and toughness, and the aluminum oxide and chromium oxide phases provide wear resistance and welding resistance.
潤滑性を高める作用をしているものである。It has the effect of increasing lubricity.
実施例
市販のＹ−ＰＳＺ （１次粒径が２３０人のＹ２Ｏ３を
３モル％含有したＺｒＬ）粉末、Ｍｇ−ＰＳＺ （同粒
径）ＭｇＯを３モル％含有したＺｒ０ｉ）粉末、Ｙ−Ｙ
ｂ−ＰＳＺ （同粒径のＹ２Ｏ，を２モル％とＹｂ２０
３１モル％を含有したＺｒ０ｘ）粉末、平均粒径０．４
μｍのＡＩ２．０．粉末＋９９．９９％）、平均粒径］
、２μｍのＣｒ１ｅｓ粉末、平均粒径 １５μｍのカー
ボニルＮ１粉末、平均粒径２０μｍのＣｒｚＣ＊粉末を
用いて第１表の如くに配合した。第１表に示したそれぞ
れの配合粉末をＺ「０．製ボールと共にポリウレタンで
内張すした容器に入れ、メタノールによる湿式混合を４
８時間行った。これらの混合粉末を第１表に併記した条
件でホットプレス焼結（）Ｉ−Ｐｌ又は１ ｔｏｎ／ｃ
ｍ”の圧力でラバープレス後、真空（約！０−’Ｔｏｒ
ｒ）もしくは雰囲気焼結して本発明の焼結体及び本発明
を外れた比較の焼結体を得た。この内、一部の試料につ
いては、焼結後にさらにＡ「ガス中、１５００ａｔｍの
圧力、 １３５０℃−１時間の条件で熱間静水圧加圧処
理（ＨＩＰ処理）を行った。Examples Commercially available Y-PSZ (ZrL containing 3 mol% of Y2O3 with a primary particle size of 230) powder, Mg-PSZ (same particle size) ZrOi) powder containing 3 mol% of MgO, Y-Y
b-PSZ (Y2O of the same particle size, 2 mol% and Yb20
Zr0x) powder containing 31 mol%, average particle size 0.4
μm AI2.0. powder +99.99%), average particle size]
, 2 μm Cr1es powder, carbonyl N1 powder with an average particle size of 15 μm, and CrzC* powder with an average particle size of 20 μm were mixed as shown in Table 1. Each blended powder shown in Table 1 was placed in a container lined with polyurethane together with a ball made of Z0.
I went for 8 hours. These mixed powders were hot press sintered () I-Pl or 1 ton/c under the conditions listed in Table 1.
After pressing the rubber at a pressure of
r) Alternatively, sintering was performed in an atmosphere to obtain a sintered body of the present invention and a comparative sintered body other than the present invention. After sintering, some of the samples were further subjected to hot isostatic pressing (HIP treatment) under the conditions of 1500 atm pressure and 1350° C. for 1 hour in A gas.
こうして得た第１表に示した本発明品１〜９及び比較品
１〜６の焼結体の硬さ、抗折力を測定すると共に、それ
ぞれの組織を観察して、その結果を第２表に示した。The hardness and transverse rupture strength of the thus obtained sintered bodies of the invention products 1 to 9 and comparative products 1 to 6 shown in Table 1 were measured, and the respective structures were observed, and the results were compared to the second Shown in the table.
第２表の内、本発明品５〜９及び比較品ｌ。In Table 2, products 5 to 9 of the present invention and comparative product 1.
２，３．５．６を用いて、下記（＾ｌ 、 （Ｂｌ 、
ｆｃｌの条件でもって摩擦試験を行い、その結果を第
３表にホした。Using 2, 3.5.6, the following (^l, (Bl,
A friction test was conducted under fcl conditions, and the results are shown in Table 3.
（Ａ） Ａρを相手材とした湿式摩擦試験試験液 エ
マルジョンタイプ
試料形状 ６．２ Ｘ ＩＯＸ １６ｍｍ相手材 缶用
ｉ材（３５φＸ ｌＯ＋＋＋ｍｌ荷 重 ２０
ｋｇｆ
回転数Ｚｏｏ ｒｐｍ
時 間 ２０ ｍ１ｎ
（Ｂｌ炭素鋼を相手材とした油供給摩擦試験試験液 高
純度鉱油
試料形状 ６．２ Ｘ ｌＯｘ １６ｍｍ相手材５２０
Ｃ（３５φｘｌＯｍｍｌ
荷 重 ２０ ｋｇｆ
回転数２００ ｒｐｍ
時 間 ２０ ｍ１ｎ
ｔｒｙ）ステンレスを相手材とした乾式摩擦試験試料形
状 ６゜２ ｘ ＩＯＸ １６ｍｍ相手材
荷 重
回転数
時 間
５ＵＳ３０４ Ｆ３５φ
ｋｇｆ
２００ ｒｐｍ
２０ ｍｉｎ
ｌｏｍｍｌ
以下余白
次に、第２表の焼結体の内、本発明品１．２゜３．４．
８及び比較品２．３．４を用いて、下記（ＤＪ及び（Ｅ
）の条件でもって切削試験を行い、その結果を第４表に
示した。(A) Wet friction test test liquid using Aρ as mating material Emulsion type sample shape 6.2 X IOX 16mm mating material I material for cans (35φX lO+++ml load 20
kgf Rotation speed Zoo rpm Time 20 m1n (Oil supply friction test test liquid using Bl carbon steel as counterpart material High purity mineral oil Sample shape 6.2
C (35 φ Margins below Next, among the sintered bodies in Table 2, the products of the present invention 1.2°3.4.
8 and comparative product 2.3.4, the following (DJ and (E
) A cutting test was conducted under the following conditions, and the results are shown in Table 4.
（Ｂｌ乾式旋削試験
チップ形状 ５ＮＧＮ １２０４０８
被 削 材 ５４８Ｃ
切削速度 ４００ ｍ／ｍｉｎ
切込み量 １．５ ｍｍ
送 リ ０．２ 開／ｒｅ
ｖ評 価 １０分間切削後の平均逃げ面摩耗量ｆＶ
、）を求める。但し、途
中で欠損又はｖ８が０．４ｍｍになっ
た場合は中止。(Bl dry turning test chip shape 5NGN 120408 Work material 548C Cutting speed 400 m/min Depth of cut 1.5 mm Feed 0.2 Open/re
v Evaluation Average flank wear fV after 10 minutes of cutting
, ). However, if there is a defect or V8 becomes 0.4 mm during the process, it will be canceled.
（Ｅｌ乾式フライス試験
チップ形状 ５ＮＧＮ １２０４０８
被 削 材 ＦＣＤ５０ （３００Ｘ １５０
ｍｍの面）切削速度 １４０ ｍ／ｍｉｎ
切込み３１ １．５ ｍｍ
評 価 送り０．１ ｍｍ／ｒｅｖから切削し、３
００ Ｘ １５Ｇ ｍｍの面が切削完了すると送りを増
加し、切削可能な
最大の送りで表示。(El dry milling test chip shape 5NGN 120408 Work material FCD50 (300X 150
mm surface) Cutting speed 140 m/min Depth of cut 31 1.5 mm Evaluation Cutting from feed 0.1 mm/rev, 3
When the surface of 00 x 15G mm has been cut, the feed is increased and the maximum feed that can be cut is displayed.
第４表
こと、摩擦係数が低い傾向にあること、摩擦試験時にお
ける相手材への損傷量が少ない傾向にあること、並びに
切削工具として用いた場合に、耐摩耗性がすぐれた傾向
にあること、高い耐溶着性、潤滑性の影響により耐欠損
性が顕著にすぐれているという効果があることから、産
業上有用な焼結体である。As shown in Table 4, the coefficient of friction tends to be low, the amount of damage to the mating material during friction tests tends to be small, and the wear resistance tends to be excellent when used as a cutting tool. It is an industrially useful sintered body because it has high welding resistance and remarkable chipping resistance due to the influence of lubricity.
特許出願人 東芝タンガロイ株式会社 （発明の効果）Patent applicant: Toshiba Tungaloy Corporation (Effect of the invention)
Claims (5)
固溶体の中の少なくとも１種を１〜５モル％含有する酸
化ジルコニウム１０〜８５重量％と酸化クロム１０〜７
２重量％と酸化アルミニウム５〜８０重量％とでなる金
属酸化物相と不可避不純物とからなることを特徴とする
高耐摩耗性複合焼結体。(1) 10 to 85% by weight of zirconium oxide and 10 to 7% by weight of chromium oxide containing 1 to 5 mol% of at least one of MgO, CaO, rare earth oxides, and mutual solid solutions thereof
A highly wear-resistant composite sintered body comprising a metal oxide phase consisting of 2% by weight of aluminum oxide and 5 to 80% by weight of aluminum oxide, and inevitable impurities.
になっていることを特徴とする特許請求の範囲第１項記
載の高耐摩耗性複合焼結体。(2) The highly wear-resistant composite sintered body according to claim 1, wherein a part or all of the zirconium oxide is tetragonal.
らの１部又は全部が相互固溶体になっていることを特徴
とする特許請求の範囲第１項又は第２項記載の高耐摩耗
性複合焼結体。(3) The high wear-resistant composite sintered product according to claim 1 or 2, wherein a part or all of the chromium oxide and the aluminum oxide are mutually solid solution. body.
％以下がＣｒ、Ｃｏ、Ｎｉ、Ｆｅ及びこれらの相互合金
の中の少なくとも１種の金属相で置換されていることを
特徴とする特許請求の範囲第１項、第２項又は第３項記
載の高耐摩耗性複合焼結体。(4) The metal oxide phase is characterized in that 10% by weight or less of the metal oxide phase is replaced with at least one metal phase selected from Cr, Co, Ni, Fe, and mutual alloys thereof. A highly wear-resistant composite sintered body according to claim 1, 2, or 3.
％以下が炭化クロムで置換されていることを特徴とする
特許請求の範囲第１項、第２項、第３項又は第４項記載
の高耐摩耗性複合焼結体。(5) The metal oxide phase is characterized in that 30% by weight or less of the metal oxide phase is substituted with chromium carbide. Highly wear-resistant composite sintered body according to item 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2210600A JP3064350B2 (en) | 1990-08-08 | 1990-08-08 | High wear resistant composite sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2210600A JP3064350B2 (en) | 1990-08-08 | 1990-08-08 | High wear resistant composite sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0492857A true JPH0492857A (en) | 1992-03-25 |
| JP3064350B2 JP3064350B2 (en) | 2000-07-12 |
Family
ID=16592014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2210600A Expired - Fee Related JP3064350B2 (en) | 1990-08-08 | 1990-08-08 | High wear resistant composite sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3064350B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6274524B1 (en) * | 1997-04-25 | 2001-08-14 | Kyocera Corporation | Semiconductive zirconia sintering body and electrostatic removing member constructed by semiconductive zirconia sintering body |
| JP2008532915A (en) * | 2005-03-15 | 2008-08-21 | サン−ゴベン・セントル・ドゥ・レシェルシェ・エ・デチュード・ユーロペアン | Gasification reactor internal lining |
-
1990
- 1990-08-08 JP JP2210600A patent/JP3064350B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6274524B1 (en) * | 1997-04-25 | 2001-08-14 | Kyocera Corporation | Semiconductive zirconia sintering body and electrostatic removing member constructed by semiconductive zirconia sintering body |
| US6602813B2 (en) * | 1997-04-25 | 2003-08-05 | Kyocera Corporation | Electrostatic removing member having semiconductive zirconia sintered body |
| JP2008532915A (en) * | 2005-03-15 | 2008-08-21 | サン−ゴベン・セントル・ドゥ・レシェルシェ・エ・デチュード・ユーロペアン | Gasification reactor internal lining |
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|---|---|
| JP3064350B2 (en) | 2000-07-12 |
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