JPS5812334B2 - Manufacturing method of hard sintered alloy - Google Patents
Manufacturing method of hard sintered alloyInfo
- Publication number
- JPS5812334B2 JPS5812334B2 JP55122956A JP12295680A JPS5812334B2 JP S5812334 B2 JPS5812334 B2 JP S5812334B2 JP 55122956 A JP55122956 A JP 55122956A JP 12295680 A JP12295680 A JP 12295680A JP S5812334 B2 JPS5812334 B2 JP S5812334B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- boride
- alloy
- iron
- mixed
- 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
Links
- 229910045601 alloy Inorganic materials 0.000 title claims description 58
- 239000000956 alloy Substances 0.000 title claims description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims description 100
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 60
- 229910052742 iron Inorganic materials 0.000 claims description 29
- 239000012071 phase Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- -1 Zr1Hf Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 3
- 238000000748 compression moulding Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000011651 chromium Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000009692 water atomization Methods 0.000 description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229910015173 MoB2 Inorganic materials 0.000 description 2
- 229910033181 TiB2 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019742 NbB2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Description
【発明の詳細な説明】
本発明は鉄を含む硼化物または複硼化物を硬質相として
含み、Ｆｅ１原子の周期率表でＶ−ａ族金属のＴｉ，Ｚ
ｒ，Ｈｆ，Ｖ−ａ族金属のＶ１Ｎｂ１Ｔａ，Ｖ−ａ族金
属のＣｒ，Ｍｏ１Ｗおよびこれらの混合物の１種または
２種以上の金属か合金あるいは、これらの金属を主成分
とする合金よりなる結合相を含む新規な硬質焼結合金の
製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention contains iron-containing borides or complex borides as a hard phase, and contains metals of group Va such as Ti and Z in the periodic table of Fe1 atoms.
A bond made of one or more metals or alloys of r, Hf, Va group metals V1Nb1Ta, Va group metals Cr, Mo1W, and mixtures thereof, or alloys containing these metals as main components. The present invention relates to a method for manufacturing a novel hard sintered alloy containing a phase.
本発明方法による合金は高速度鋼と同等、もしくはそれ
以上の高硬度を有し、かつ高い強度を有する緻密な焼結
合金であり、また常温および高温での耐食性、耐酸化性
も優れた特徴を有する。The alloy produced by the method of the present invention is a dense sintered alloy with high hardness equal to or higher than that of high-speed steel and high strength, and also has excellent corrosion resistance and oxidation resistance at room and high temperatures. has.
更に、従来から実用きれているＷＣ系超硬合金と比較し
て、匹敵し得る硬度と強度をもつ焼結合金を得ることが
可能であり、かつ資源的に豊富な鉄やクロム等の元素を
多く含むので安価に製造できる上に、比重は７〜７．５
程度でＷＣ系超合金の約１／２であり、軽いという特徴
を有する。Furthermore, it is possible to obtain a sintered alloy with comparable hardness and strength compared to WC-based cemented carbide, which has been in practical use for a long time, and it is possible to obtain a sintered alloy with comparable hardness and strength, and it is also possible to obtain a sintered alloy that has abundant resources such as iron and chromium. It can be manufactured at low cost because it contains a large amount, and its specific gravity is 7 to 7.5.
It is about 1/2 the weight of WC superalloys, and is characterized by its light weight.
上記の特徴から本発明方法による合金は、耐摩耗性、耐
食性、耐熱性、耐酸化性あるいはこれらの特性を具備し
た材料として、引き抜き等の各種ダイス、切削工具、切
断工具、としての打ち抜き金型やプレス金型、スリツタ
ーの刃やその他の刃物等の広範囲の用途に利用できる。Due to the above characteristics, the alloy produced by the method of the present invention has wear resistance, corrosion resistance, heat resistance, oxidation resistance, or as a material with these characteristics, it can be used as a punching die for various dies such as drawing, cutting tools, cutting tools, etc. It can be used for a wide range of applications such as press molds, slitter blades, and other cutlery.
本発明方法による合金は４０〜９６重量係の硬質相と、
４〜６０重量係の結含相よりなる。The alloy according to the method of the invention has a hard phase having a weight ratio of 40 to 96%;
It consists of a condensed phase of 4 to 60% by weight.
前記硬質相は鉄硼化物、もしくはその一部を１種または
２種以上の非鉄元素を含む鉄系複硼化物、非鉄元素の硼
化物あるいは非鉄元素の複硼化物の１種または２種以上
で置き換えた少なくとも２０重量係以上の鉄元素を含む
複硼化物である。The hard phase is an iron boride, or a part thereof is an iron-based complex boride containing one or more non-ferrous elements, a boride of a non-ferrous element, or one or more complex borides of a non-ferrous element. It is a complex boride containing at least 20 or more parts by weight of the iron element.
ここでいう非鉄元素とはＶ−ａ族、ｖ−ａ族、Ｖ−ａ族
に含まれるＴｉ．Ｚｒ．Ｈｆ，Ｖ，Ｎｂ１Ｔａ，Ｃｒ１
Ｍｏ，Ｗの各元素および■族のＮｉ，ＣＯ、■一ａ族の
Ｍｎおよび非金属元素である０１Ｎ１Ｐである。The non-ferrous elements mentioned here include Ti, which is included in the V-a group, the V-a group, and the V-a group. Zr. Hf, V, Nb1Ta, Cr1
These are the elements Mo and W, Ni and CO of group 1, Mn of group 1a, and 01N1P, which is a nonmetallic element.
またこれらの元素の他にもＬｉ，Ｎａ，Ｋなどのアルカ
リ金属、Ｂｅ，Ｍｇ．Ｃａ１Ｓｒ，Ｂａなどのアルカリ
士類金属、Ｌａ１Ｃｅなどのランタン系元素、ＴｈｖＮ
）ｖなどのアクチニウム系元素、Ｒｕ，Ｒｈなどの■族
元素などの硼化物があり、これらの少量を添加し、また
は不純物として含まれることは可能であり、こりらが少
量含まれることをさまたげるものではない。In addition to these elements, alkali metals such as Li, Na, and K, Be, Mg. Alkali metals such as Ca1Sr and Ba, lanthanum elements such as La1Ce, ThvN
) There are borides such as actinium-based elements such as V, group II elements such as Ru and Rh, and it is possible to add small amounts of these elements or to include them as impurities, and to prevent these from being included in small amounts. It's not a thing.
結合相はＦｅ１Ｃｒ，Ｍｏ，Ｗ．Ｔｉ，Ｚｒ，Ｈｆ，Ｖ
１Ｎｂ，Ｔａ，から選ばれる金属、あるいはこれらの合
金、またはこれらの金属または合金を主成分としＮｉ，
Ｃｕ，Ｃｏ，Ｍｎ，Ｐ１Ｃのうち１種以上を補助成分と
する合金の１種または２種以上よりなる。The bonded phase is Fe1Cr, Mo, W. Ti, Zr, Hf, V
A metal selected from 1Nb, Ta, or an alloy thereof, or a metal or alloy containing these metals or alloys as a main component, and Ni,
It is made of one or more alloys containing one or more of Cu, Co, Mn, and P1C as an auxiliary component.
硬質相および結合相の範囲を上記の範囲に限定したのは
、硬質相が４０重量φ未満では硬度が不足し、結合相が
４重量係未満では靭性が不足するからである。The range of the hard phase and the binder phase is limited to the above ranges because if the hard phase is less than 40% by weight, the hardness is insufficient, and if the binder phase is less than 4% by weight, the toughness is insufficient.
また硬質相となる硼化物中の鉄元素の含有量は２０重量
係以上、好ま１くは３０重量係以上とすることが望まし
い。Further, it is desirable that the content of the iron element in the boride serving as the hard phase is 20 parts by weight or more, preferably 10 parts by weight or more.
また鉄の上限は９６．８重量係である。The upper limit for iron is 96.8 weight ratio.
この理由は、鉄を含有する複硼化物の焼結体が充分に高
い硬度と靭性を示すこと、ＣｒやＭｏなどの適量添加に
よってステンレス鋼と同様の優れた耐食性と耐熱性、耐
酸化性を糸すこと、鉄を主とした硼化物粉末は工業的に
容易に作ることができること、鉄は資源的に豊富であり
、かつ最も安価であることによる。The reason for this is that the sintered body of complex boride containing iron exhibits sufficiently high hardness and toughness, and that by adding appropriate amounts of Cr and Mo, it has excellent corrosion resistance, heat resistance, and oxidation resistance similar to that of stainless steel. This is because iron-based boride powder can be easily produced industrially, and iron is an abundant resource and is the cheapest.
焼結合金中のＢの含有量は３〜２０重量係、好ましくは
４〜１７重量係である。The content of B in the sintered alloy is 3 to 20 parts by weight, preferably 4 to 17 parts by weight.
Ｂ量が３％より少ないと、硬度が目的とする高硬度に達
しなくなる。If the amount of B is less than 3%, the hardness will not reach the desired high hardness.
逆にＢ量が多過ぎると抗折力の低下をもたらし、充分な
靭性を得ることが困難になるので上限は２０飴である。On the other hand, if the amount of B is too large, the transverse rupture strength will decrease and it will be difficult to obtain sufficient toughness, so the upper limit is 20 pieces.
鉄一硼素系合金は溶解鋳造することが可能であるが、鋳
造された合金は非常に脆く、また熱間や冷間の加工が困
難であり、機械加工も困難であるために実用に供し難い
。Iron-boron alloys can be melted and cast, but the cast alloys are extremely brittle, difficult to hot or cold work, and difficult to machine, making them difficult to put to practical use. .
また、ＺｒＢ２ＡＭｏＢ２（融点２１００℃）、ＴｉＢ
２（融点２８００〜３０００Ｃ）、ＷＢ（融点２４００
〜２８００℃）やＮｂＢ２（融点３０００℃）などを硬
質相として多く含有する成分は通常の加熱溶解法では、
硼化物の融点が高過ぎるために、溶解法に困難が伴なう
。In addition, ZrB2AMoB2 (melting point 2100°C), TiB
2 (melting point 2800-3000C), WB (melting point 2400C)
- 2800℃) and NbB2 (melting point 3000℃) as hard phases can be melted using normal heat melting method.
The melting point of boride is too high, making the dissolution process difficult.
本発明方法では、粉末冶金法を用い、焼結合金とするこ
とによって合金に充分な強度を与え、最終的な所望の形
状を持った硬質合金を容易に作ることができる。In the method of the present invention, by using a powder metallurgy method and forming a sintered alloy, sufficient strength is imparted to the alloy, and a hard alloy having a final desired shape can be easily produced.
本発明の硬質合金は、鉄を含む硼化物合金粉末と金属粉
末を混合後、圧粉成型し、焼結して製造される。The hard alloy of the present invention is manufactured by mixing iron-containing boride alloy powder and metal powder, compacting the mixture, and sintering the mixture.
焼結の際に硼化物相と金属相間に共晶液相を生じること
によって、緻密な焼結合金が容易に得られる。By generating a eutectic liquid phase between the boride phase and the metal phase during sintering, a dense sintered alloy can be easily obtained.
したがって結合相の中には少量の硼素が含有されるもの
と考えられる。Therefore, it is considered that a small amount of boron is contained in the binder phase.
また硼化物合金粉末中の金属成分を硼化物生成量よりも
過剰に含有させておけば、結合相としての金属粉末を添
加混合することなしに焼結して製造することも可能であ
る。Furthermore, if the metal component in the boride alloy powder is contained in excess of the amount of boride produced, it is also possible to manufacture by sintering without adding and mixing metal powder as a binder phase.
本発明の硬質焼結合金の製造法において、合金中の硬質
相を形成する硼化物粉末は所望の元素を含有させた溶融
合金を細孔から落下させ、ノズルから噴出する高圧の水
流またはアルゴンガスや窒素ガスによって粉砕する、い
わゆる水アトマイズ法または、ガスアトマイズ法によっ
て作ることが工業的に有利であるが、その他の粉末製造
法を利用してもよい。In the method for producing a hard sintered alloy of the present invention, the boride powder that forms the hard phase in the alloy is produced by dropping a molten alloy containing desired elements through pores, and then using a high-pressure water stream or argon gas jetted from a nozzle. Although it is industrially advantageous to produce powder by the so-called water atomization method or gas atomization method, in which the powder is pulverized using nitrogen gas, other powder production methods may also be used.
このようにして作られた硬質硼化物合金粉末に、結合相
を形成させる金属粉末を混合し．て圧粉成形して所望の
形の圧粉体とし、この圧粉体を真空中または水素ガスや
アルゴンガス等の還元性雰囲気や不活性雰囲気中で加熱
し、一部液相を生成させることによって、焼結体の密度
を上昇させる。The hard boride alloy powder thus produced is mixed with metal powder to form a binder phase. The powder compact is compacted into a desired shape, and the compact is heated in a vacuum or in a reducing atmosphere such as hydrogen gas or argon gas, or in an inert atmosphere to partially generate a liquid phase. This increases the density of the sintered body.
しかしながら、ＴｉＢ２やＷＢＳＮｂＢ２、ＺｒＢ２、
やＭｏＢ２などの高融点の硼化物を多く含む硬質硼化物
合金粉末は、これらの合金を加熱溶解して、水やガスで
粉砕するアトマイズ法では、溶解温度を非常な高温とし
なければならないので、粉末の製造法に困難が伴なう。However, TiB2, WBSNbB2, ZrB2,
For hard boride alloy powders containing a large amount of high-melting-point borides, such as MoB2 and MoB2, the melting temperature must be extremely high in the atomization method, in which these alloys are melted by heating and pulverized with water or gas. Difficulties arise in the method of manufacturing the powder.
その他の気相硼化法なども工業的な実施について問題が
ある。Other methods such as vapor phase boronization also have problems in industrial implementation.
この点に関して、本発明者らは、低融点の鉄硼化物およ
び鉄系複硼化物合金粉末に、高融点硼化物を生成する元
素の粉末や金属粉末を添加し、混合して、圧粉、成形後
焼結し、焼結中こ高融点の硼化物を生成させ、同時に焼
結も完了させるととができるということを見出した。In this regard, the present inventors added powders of elements and metal powders that produce high-melting-point borides to low-melting-point iron boride and iron-based complex boride alloy powders, mixed them, and compacted powder. It has been found that it is possible to sinter after molding, generate a boride with a high melting point during sintering, and complete sintering at the same time.
すなわち、製造が容易でかつ比較的低融点の鉄硼化物粉
末または鉄系複硼化物合金粉末に、Ｍｏ，Ｗ・・・・・
・合金粉末」とあるのを「鉄硼化物よりも高融点の硼化
物を生成し得るＣ粉末ミまたはＭｏ１Ｗ，Ｃｒ，Ｔｉ，
Ｚｒ，Ｈｆ１Ｖ１Ｎｂ，Ｔａから選ばれる金属粉末ある
いはＣｒ，Ｍｏ，Ｗ，Ｔｉ１Ｚｒ．Ｈｆ，Ｖ，Ｎｂ，Ｔ
ａおよびＦｅの合金粉末、もしくはＣｒ’ＭＯ％Ｗ１Ｔ
ｔ％ＺｒＮＨｆ，Ｖ、Ｎｂ，ＴａおよびＦｅを主成分と
しＮｉ１Ｃｕ，Ｃｏ，Ｍｎ，Ｐ，Ｃのうち１種以上を補
助成分とする合金粉末を添加混合し、圧粉、成形後焼結
する。That is, Mo, W...
・Alloy powder” is replaced with “C powder, Mo1W, Cr, Ti, which can produce boride with a higher melting point than iron boride.
Metal powder selected from Zr, Hf1V1Nb, Ta or Cr, Mo, W, Ti1Zr. Hf, V, Nb, T
a and Fe alloy powder or Cr'MO%W1T
An alloy powder containing t%ZrNHf, V, Nb, Ta, and Fe as main components and one or more of Ni1Cu, Co, Mn, P, and C as auxiliary components is added and mixed, and the powder is compacted, shaped, and sintered.
焼結の際に鉄硼化物と高融点硼化物生成元素との反応に
より、高融点硼化物を生成させ、同時に液相を生じさせ
、がつ適量の結合相を残すように粉末の混合比を選ぶこ
とにより、高硬度で強度も高い、緻密な焼結合金を作る
ことができるのである。During sintering, the mixing ratio of the powder is adjusted so that a high melting point boride is generated by the reaction between iron boride and a high melting point boride forming element, and at the same time a liquid phase is generated, leaving an appropriate amount of binder phase. By selecting the right material, it is possible to create a dense sintered alloy with high hardness and strength.
上記のようにして作った高融点硼化物を含有する焼結体
を低密度としておき、これを再粉砕して粉末とし、この
粉末に結合材となる金属または合金粉末を添加混合して
圧粉し、焼結して硬質焼結合金としてもよい。The sintered body containing the high melting point boride prepared as above is made into a low-density powder, which is re-pulverized into a powder, and a metal or alloy powder as a binder is added to this powder and mixed to form a powder. However, it may be sintered to form a hard sintered alloy.
本発明方法による硬質焼結合金は、液相焼結によって焼
結体を高密度化するが、熱間静水圧プレス法、熱間プレ
ス法、熱間鍛造法や放電焼結法などの方法によって、あ
るいはこれらの方法を液相焼結法と併用する方法によっ
て高密度焼結体を作ることもできる。The hard sintered alloy produced by the method of the present invention is produced by densifying the sintered body by liquid phase sintering. Alternatively, a high-density sintered body can be produced by combining these methods with a liquid phase sintering method.
また常温での耐食性、高温での耐酸化性、耐熱性をより
向上させるためには、硬質相にＣｒやＭｏ，Ｎｉ等の合
金元素を含有させることが有効である。Further, in order to further improve corrosion resistance at room temperature, oxidation resistance and heat resistance at high temperatures, it is effective to include alloying elements such as Cr, Mo, and Ni in the hard phase.
また結合金属材としてＣｒ粉末やＭｏ粉末を用いること
も同様に効果がある。Furthermore, using Cr powder or Mo powder as the bonding metal material is similarly effective.
次に本発明を実施例により説明する。Next, the present invention will be explained by examples.
実施例 １
鉄、フエロポロンおよびフエ口クロムを原料として高周
波炉により溶解した溶湯を水圧７０ｋＶ／ＣＩ！で水ア
トマイズにより粉砕して、Ｂ７．８重量係、Ｃｒｌｌ．
７重量係、残部は鉄および少量の不純物よりなる粒度８
０メッシュ以下の硼化物合金粉末を作成した。Example 1 Molten metal made from iron, ferroporon, and ferrochrome as raw materials was melted in a high-frequency furnace at a water pressure of 70 kV/CI! It was crushed by water atomization to give B7.8 weight, Crll.
Particle size: 7 by weight, the remainder consisting of iron and a small amount of impurities
A boride alloy powder with a size of 0 mesh or less was created.
この硼化物合金粉末とＣｒ粉末、Ｎｉ粉末およびＷ粉末
を９０：５：３：２の重量係で配合し、ボールミルによ
り、エチルアルコール溶液を用いて、４８時間湿式混合
微粉砕した後、真空乾燥をおこないＡ３ｔ／ｃＩ！め成
形圧力で圧粉した成形体を、１０””ｉｉＨｇの真空中
で１１７０℃で３時間焼結した。This boride alloy powder, Cr powder, Ni powder and W powder were mixed in a weight ratio of 90:5:3:2, wet mixed and pulverized for 48 hours using an ethyl alcohol solution in a ball mill, and then vacuum dried. Perform A3t/cI! The compact was compacted under a compacting pressure and sintered at 1170°C for 3 hours in a vacuum of 10''iiHg.
抗折力１３０ｋｇ／ｍｍ２，硬度ＨＲＡ８５を示す密な
焼結体が得られた。A dense sintered body having a transverse rupture strength of 130 kg/mm 2 and a hardness of HRA 85 was obtained.
実施例 ２
実施例１の鉄系複硼化物合金粉末９０重量係に対し、Ｎ
ｉ，１．３重量係、Ｍｏ０．６重量係、Ｃｕ１．６重量
係残部はＦｅよりなる鉄合金粉末を１０重量係の割合で
配合し、ボールミルにより４８時間湿式混合し微粉砕し
た後、真空乾燥した粉末を３ｔ／ｃＩ／の成形圧力で圧
粉し、成形体を真空中１１８０℃において３時間焼結し
た。Example 2 N
i, 1.3 weight ratio, Mo 0.6 weight ratio, Cu 1.6 weight ratio, iron alloy powder consisting of Fe is blended at a ratio of 10 weight ratio, wet mixed in a ball mill for 48 hours, finely pulverized, and then vacuum The dried powder was compacted at a compacting pressure of 3 t/cI/, and the compact was sintered in vacuum at 1180° C. for 3 hours.
抗折力１２０ｋｇ／ｍｍ２、硬度ＨＲＡ８３を示す緻密
な焼結体が得られた。A dense sintered body having a transverse rupture strength of 120 kg/mm2 and a hardness of HRA83 was obtained.
実施例 ３
実施例１の鉄系複硼化物合金粉末とＣｒ粉末を９０：１
０の重量係で配合し、ボールミルにより４８時間湿式混
合微粉砕したあと、真空乾燥をおこなった粉末を３ｔ／
ｃＩ１の成形圧力で圧粉し、成形体を真空中１２００℃
において３時間焼結した。Example 3 The iron-based complex boride alloy powder of Example 1 and the Cr powder were mixed in a ratio of 90:1.
The powder was mixed at a weight ratio of 0, wet mixed and pulverized for 48 hours using a ball mill, and then vacuum dried.
The powder is compacted at a molding pressure of cI1, and the molded body is heated at 1200°C in a vacuum.
It was sintered for 3 hours.
抗折力１１５ｋｙ／ｍｍ４、硬度ＨＲＡ８４を示す密な
焼結体が得られた。A dense sintered body having a transverse rupture strength of 115 ky/mm4 and a hardness of HRA84 was obtained.
実施例 ４
鉄、フエロボロン、フエ口クロムを原料として高周波溶
解炉で溶解した溶湯を水アトマイズ法により粉砕してＢ
１６．６重量係、Ｃｒ９．５重量係、残部は鉄よりなる
組成と８０メッシュ以下の粒度を有する鉄系硼化物合金
粉末を作成した。Example 4 A molten metal made of iron, ferroboron, and ferrochromium as raw materials was melted in a high-frequency melting furnace and pulverized by water atomization.
An iron-based boride alloy powder was prepared having a composition of 16.6% by weight, 9.5% by weight of Cr, the balance being iron, and a particle size of 80 mesh or less.
この硼化■合金粉末とＭｏ粉末、Ｃｒ粉末、Ｔｉ粉末お
よびＦｅ粉末を重量係で４５：２７：１２：７：９にて
配合し、ボールミルで４８時間湿式混合粉砕した後、真
空乾燥をおこなった。This boride alloy powder, Mo powder, Cr powder, Ti powder, and Fe powder were mixed in a weight ratio of 45:27:12:7:9, wet mixed and ground in a ball mill for 48 hours, and then vacuum dried. Ta.
得られた粉末を３ｔ／ｉｍ２の圧力で、圧粉成形し、真
空中１３００℃において、２時間焼結した。The obtained powder was compacted at a pressure of 3 t/im 2 and sintered in vacuum at 1300° C. for 2 hours.
抗折力１００ｋｇ／ｒｎ４、硬度ＨＲＡ８９を示す緻密
な焼結合金が得られた。A dense sintered alloy having a transverse rupture strength of 100 kg/rn4 and a hardness of HRA 89 was obtained.
実施例 ５
実施例４の鉄系硼化物合金粉末とＴｉ粉末およびＦｅ粉
末を重量係で７０：２０：１０に配合し、ボールミルで
４８時間湿式混合粉砕したあと、真空乾燥をおこなった
。Example 5 The iron-based boride alloy powder of Example 4, Ti powder, and Fe powder were mixed in a weight ratio of 70:20:10, wet mixed and ground in a ball mill for 48 hours, and then vacuum dried.
得られた粉末を３ｔ／ｆｆｌの圧力で圧粉成形し、１３
００℃で２時間真空中で焼結した。The obtained powder was compacted at a pressure of 3t/ffl, and
Sintering was carried out in vacuum at 00°C for 2 hours.
抗折力７８ｋｇ／ｍｍ２，硬度ＨＲＡ８５の緻密な焼結
体が得られた。A dense sintered body with a transverse rupture strength of 78 kg/mm 2 and a hardness of HRA 85 was obtained.
この焼結体をＸ線回析により同定した。This sintered body was identified by X-ray diffraction.
同定の結果はＦｅ２ＢＮＴｔＢ２、Ｔｉと少量のＦｅの
存在が確認された。The identification results confirmed the presence of Fe2BNTtB2, Ti, and a small amount of Fe.
ＦｅＢの存在は認められなかった。The presence of FeB was not recognized.
低融点の鉄硼化物であるＦｅＢ（融点１５４０Ｃ）を含
む鉄系硼化物合傘粉末と、Ｔｉ粉末が焼結中に反応し、
高融点硼化物であるＴｉＢ２（融点２９８０Ｃ）を生成
したことが確認された。Iron-based boride compound powder containing FeB (melting point 1540C), which is a low melting point iron boride, and Ti powder react during sintering,
It was confirmed that TiB2 (melting point: 2980C), which is a high melting point boride, was produced.
実施例 ６
実施例４の鉄系硼化物合金粉末とＭｏ粉末、Ｃｒ粉末、
Ｚｒ粉末、Ｆｅ粉末およびＮｉ粉末を重量係で４８：２
５：１０：７：８：２に配合し、ボールミルで４８時間
湿式混合粉砕したあと、真空乾燥をおこなった。Example 6 Iron-based boride alloy powder of Example 4, Mo powder, Cr powder,
Zr powder, Fe powder and Ni powder in a weight ratio of 48:2
The mixture was mixed in a ratio of 5:10:7:8:2, wet mixed and ground in a ball mill for 48 hours, and then vacuum dried.
得られた粉末を３ｔ／ｆｆｌの圧力で圧粉成形し、真空
中で１３５０℃において２時間焼結した。The obtained powder was compacted at a pressure of 3 t/ffl and sintered in vacuum at 1350° C. for 2 hours.
抗折力６８ｋｇ／ｍＡ２，硬度ＨＲＡ９０の焼結体が得
られた。A sintered body having a transverse rupture strength of 68 kg/mA2 and a hardness of HRA90 was obtained.
実施例 ７
実施例４の鉄系硼化物合金粉末と、ＭＯ粉末、Ｎｂ粉末
、Ｔｉ粉末、Ｃｒ粉末および低炭素鋼粉末を重量係で４
３：１９：７：７：１１：１３に配合し、ボールミルで
４８時間湿式混合粉砕したあと、真空乾燥をおこなった
。Example 7 The iron-based boride alloy powder of Example 4, MO powder, Nb powder, Ti powder, Cr powder, and low carbon steel powder were mixed in a weight ratio of 4.
The mixture was mixed at a ratio of 3:19:7:7:11:13, wet mixed and ground in a ball mill for 48 hours, and then vacuum dried.
得られた粉末を３ｔ／ｃｍ２の圧力で圧粉成形し、１２
５０Ｃで２時間真空中で焼結した。The obtained powder was compacted at a pressure of 3t/cm2, and
Sintering was carried out in vacuum at 50C for 2 hours.
抗折力８３ｋｇ／ｍｉ２、硬度ＨＲＡ８９の緻密な焼結
体が得られた。A dense sintered body with a transverse rupture strength of 83 kg/mi2 and a hardness of HRA 89 was obtained.
実施例 ８
実施例４の鉄系硼化物今金粉末とＭｏ粉末、Ｔｉ粉末、
Ｃｒ粉末、低炭素鋼粉末およびＴｉＣ粉末を重量係で４
５：２７：６：１２：９：１に配合し、ボールミルで４
８時間湿式混合粉砕したあと真空乾燥をおこなった。Example 8 Iron-based boride powder of Example 4, Mo powder, Ti powder,
Cr powder, low carbon steel powder and TiC powder by weight
Blend in the ratio of 5:27:6:12:9:1 and use a ball mill to
After wet mixing and pulverization for 8 hours, vacuum drying was performed.
得られた粉末を３ｔ／ｆｆｌの圧力で圧粉成形し、１３
００℃で２時間真空中で焼結した。The obtained powder was compacted at a pressure of 3t/ffl, and
Sintering was carried out in vacuum at 00°C for 2 hours.
抗折力８１ｋ９／ｍＡ２、硬度ＨＲＡ８８の緻密な焼結
体が得られた。A dense sintered body with a transverse rupture strength of 81k9/mA2 and a hardness of HRA88 was obtained.
実施例 ９
実施例４のＦｅ−１６．６％Ｂ−９．５％Ｃｒ粉末４０
重量係にＦｅ−６０％Ｃｒ粉末２３．４重量チ、Ｆｅ−
４０％Ｔｉ粉末１７．５重量係とＦｅ−６０％ＭＯ粉末
１９．１重量係を配合し、ボールミルで４８時間湿式混
合粉砕したあと真空乾燥をおこなった。Example 9 Fe-16.6%B-9.5%Cr powder 40 of Example 4
Weight section: Fe-60% Cr powder 23.4 wt.
40% Ti powder (17.5% by weight) and Fe-60% MO powder (19.1% by weight) were blended, wet mixed and ground in a ball mill for 48 hours, and then vacuum dried.
得られた粉末を３ｔ／ｃｒＬの圧力で圧粉成形し、真空
中１３００℃で１時間焼結した。The obtained powder was compacted at a pressure of 3 t/crL and sintered at 1300° C. for 1 hour in vacuum.
抗折力９５ｋｇ／ｍｉｘ，硬度ＨＲＡ８７の焼結体が得
られた。A sintered body having a transverse rupture strength of 95 kg/mix and a hardness of HRA 87 was obtained.
密度はη．０１ｇ／ｃｒｉであった。The density is η. It was 01g/cri.
実施例 １０
実施例４の鉄系硼化物合金粉末と、ＭＯ粉末、Ｃｒ粉末
、Ｎｉ粉末、Ｆｅ粉末、Ｃ粉末を重量係で４５：２８：
５：１０：１１．３：０．７に配合し、ボールミルで４
８時間湿式混合粉砕したあと、真空乾燥をおこなった。Example 10 The weight ratio of the iron-based boride alloy powder of Example 4, MO powder, Cr powder, Ni powder, Fe powder, and C powder was 45:28:
5:10:11.3:0.7 and ball mill
After wet mixing and pulverization for 8 hours, vacuum drying was performed.
得られた粉末を３ｔ／ｃｎ！の圧力で圧粉成形し、１２
７５℃で１時間真空中で焼結した。3t/cn of the obtained powder! Compacting at a pressure of 12
Sintering was carried out in vacuum at 75° C. for 1 hour.
抗折力１４０ｋｇ／ｍｍ２。Transverse rupture strength 140kg/mm2.
硬度ＨＲＡ８８の緻密な焼結体が得られた。A dense sintered body with a hardness of HRA88 was obtained.
Claims (1)
化物、ＦｅおよびＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ１Ｔａ．
Ｃｒ，Ｍ６、Ｗ，Ｎｉ，Ｃｏ．Ｍｎから選ばれた非鉄元
素の１種以上から成る、鉄系複硼化物合金粉末に、これ
らの鉄硼化物よりも高融点の硼化物を生成し得るＣ粉末
または、Ｃｒ１Ｍｏ１Ｗ，Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ
，Ｔａから選ばれる金属粉末あるいはＣｒ１Ｍｏ１Ｗ，
Ｔｉ，Ｚｒ，Ｈｆ１Ｖ．Ｎｂ，ＴａおよびＦｅの合金粉
末、もしくはＣｒ，Ｍｏ，Ｗ１Ｔｉ，Ｚｒ１Ｈｆ．Ｖ、
Ｎｂ，ＴａおよびＦｅを主成分としＮｉ．Ｃｕ，Ｃｏ，
Ｍｎ．Ｐ，Ｃのうち１種以上を補助成分とする合金粉末
の１種または２種以上を混合し、該混合時に焼結後の硬
質焼結合金の硬質相が４０〜９６重量チになる範囲の混
合比とし、湿式法によって機械的に微粉化混合をおこな
った粉末を、圧縮成形した後、真空中、還元ガス中ある
いは不活性ガス中で加熱して焼結し、該焼結中の反応に
より高融点、高硬度の硼化物または複硼化物を形成させ
、同時に液相焼結をおこなうことを特徴とする耐摩耗性
を有する該硬質焼結合金の製造法。 ２ ＦｅＢおよび／またはＦｅ２Ｂを主成分とする鉄硼
化物、ＦｅおよびＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ１Ｔａ，
Ｃｒ，Ｍｏ，Ｗ１Ｎｉ，Ｃｏ，Ｍｎから選ばれた非鉄元
素の１種以上から成る鉄系複硼化物の化学成分になるよ
うに調整して加熱落解した溶湯を、高圧の水流または不
活性ガス流によって粉砕して粉末とし、該粉末に特許請
求の範囲第１項記載の結合相を形成させるＦｅ１Ｃｒ，
Ｍｏ，Ｗ，Ｔｉ，Ｚｒ１Ｈｆ，Ｖ，Ｎｂ，Ｔａから選ば
れる金属粉末、あるいはこれらの合金粉末、またはこれ
らの金属または合金を主成分としＮｉ，Ｃｕ，Ｃｏ，Ｍ
ｎ，Ｐ，Ｃのうち１種以上を補助成分とする合金粉末の
１種または２種以上を混合し、該混合時に焼結後の硬質
焼結合金の硬質相が４０〜９６重量係になる範囲の混合
比とし、湿式法法によって機械的に微粉化混合をおこな
った粉末を、圧縮成形した後、真空中、還元ガス中ある
いは不活性ガス中で加熱することによって液相焼結をお
こなわせることを特徴とする耐摩耗性を有する該硬質焼
結合金の製造法。[Claims] 1 Iron boride containing FeB and/or Fe2B as a main component, Fe and Ti, Zr, Hf, V, Nb1Ta.
Cr, M6, W, Ni, Co. C powder or Cr1Mo1W, Ti, Zr, Hf, which can produce a boride with a higher melting point than these iron borides, is added to the iron-based complex boride alloy powder consisting of one or more non-ferrous elements selected from Mn. ,V,Nb
, Ta or Cr1Mo1W,
Ti, Zr, Hf1V. Alloy powder of Nb, Ta and Fe, or Cr, Mo, W1Ti, Zr1Hf. V,
Ni. Cu, Co,
Mn. One or more types of alloy powders containing one or more types of P and C as auxiliary components are mixed, and the hard phase of the hard sintered alloy after sintering at the time of mixing is in the range of 40 to 96 wt. After the powder is mechanically pulverized and mixed using a wet method, it is compressed and then heated and sintered in a vacuum, reducing gas, or inert gas. A method for producing a hard sintered alloy having wear resistance, which comprises forming a boride or complex boride with a high melting point and high hardness, and simultaneously performing liquid phase sintering. 2 FeB and/or Fe2B-based iron boride, Fe and Ti, Zr, Hf, V, Nb1Ta,
The molten metal, which has been heated and melted and adjusted to have a chemical composition of iron-based complex boride consisting of one or more nonferrous elements selected from Cr, Mo, W1Ni, Co, and Mn, is heated and melted using a high-pressure water stream or inert gas. Fe1Cr, which is ground into a powder by means of a flow, and which powder forms a binder phase according to claim 1;
Metal powder selected from Mo, W, Ti, Zr1Hf, V, Nb, Ta, or an alloy powder of these, or a powder containing these metals or alloys as a main component and containing Ni, Cu, Co, M
One or more types of alloy powders containing one or more types of n, P, and C as auxiliary components are mixed, and at the time of mixing, the hard phase of the hard sintered alloy after sintering becomes 40 to 96% by weight. The powder is mechanically pulverized and mixed using a wet method at a mixing ratio within a range, and after compression molding, liquid phase sintering is performed by heating in vacuum, reducing gas, or inert gas. A method for producing the hard sintered alloy having wear resistance, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55122956A JPS5812334B2 (en) | 1980-09-06 | 1980-09-06 | Manufacturing method of hard sintered alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55122956A JPS5812334B2 (en) | 1980-09-06 | 1980-09-06 | Manufacturing method of hard sintered alloy |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP49129541A Division JPS5155708A (en) | 1974-11-12 | 1974-11-12 | Koshitsushoketsugokin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5655534A JPS5655534A (en) | 1981-05-16 |
| JPS5812334B2 true JPS5812334B2 (en) | 1983-03-08 |
Family
ID=14848780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55122956A Expired JPS5812334B2 (en) | 1980-09-06 | 1980-09-06 | Manufacturing method of hard sintered alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5812334B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5950156A (en) * | 1982-09-14 | 1984-03-23 | インガ−ソル・ランド・カンパニ− | Sintered forged products and manufacture |
-
1980
- 1980-09-06 JP JP55122956A patent/JPS5812334B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5655534A (en) | 1981-05-16 |
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