JP2020152945A - Manufacturing method of heat-resistant lightweight high strength sintered body - Google Patents
Manufacturing method of heat-resistant lightweight high strength sintered body Download PDFInfo
- Publication number
- JP2020152945A JP2020152945A JP2019051005A JP2019051005A JP2020152945A JP 2020152945 A JP2020152945 A JP 2020152945A JP 2019051005 A JP2019051005 A JP 2019051005A JP 2019051005 A JP2019051005 A JP 2019051005A JP 2020152945 A JP2020152945 A JP 2020152945A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- heat
- sintered body
- less
- lightweight
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011812 mixed powder Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 21
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000009792 diffusion process Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005242 forging Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 27
- 239000000956 alloy Substances 0.000 abstract description 27
- 229910004349 Ti-Al Inorganic materials 0.000 abstract description 9
- 229910004692 Ti—Al Inorganic materials 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 description 24
- 239000010936 titanium Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 15
- 150000004767 nitrides Chemical class 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 229910010038 TiAl Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 238000000879 optical micrograph Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910018509 Al—N Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000010587 phase diagram Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910011208 Ti—N Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229910018575 Al—Ti Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001234 light alloy Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021362 Ti-Al intermetallic compound Inorganic materials 0.000 description 1
- 229910009594 Ti2AlN Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000000365 skull melting Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
本発明は、製造が容易であって、耐熱性を有する高強度で軽量なＴｉ−Ａｌ系合金を得る方法に関する。 The present invention relates to a method for obtaining a high-strength and lightweight Ti—Al alloy that is easy to manufacture and has heat resistance.
従来、Ｔｉ−Ａｌ系金属間化合物は耐熱性がある軽量材料として知られ、比強度、クリープ強度も高いことから航空機エンジン部品などに使用されている。 Conventionally, Ti-Al intermetallic compounds are known as lightweight materials having heat resistance, and are used for aircraft engine parts and the like because of their high specific strength and creep strength.
しかしながら、Ｔｉ−Ａｌ系合金は製造コストが高く、用途が限定されるという問題点があった。高コストの要因として、Ｔｉ自体が高価であるほか、融点が１７００℃程度と高くほとんど全てのるつぼ材と反応してしまい、水冷銅るつぼを用いるスカル溶解といった特殊な溶解鋳造法をとらざるを得ない点があげられる。加えて、素材由来の難切削性や低靭性が影響し、加工費増を招来してしまう。 However, the Ti—Al alloy has a problem that the manufacturing cost is high and the use is limited. As a factor of high cost, Ti itself is expensive, and the melting point is as high as about 1700 ° C, and it reacts with almost all crucible materials, so we have to take a special melting casting method such as skull melting using a water-cooled copper crucible. There is no point. In addition, the difficult-to-cut property and low toughness derived from the material have an effect, which leads to an increase in processing cost.
一方、従来のＴｉ−Ａｌ系合金は、９００℃超にて著しい強度低下が見られ、使用温度範囲がせいぜい１０００℃未満に限定されるという問題点があった。 On the other hand, the conventional Ti—Al alloy has a problem that the strength is significantly lowered above 900 ° C. and the operating temperature range is limited to less than 1000 ° C. at most.
なお、本願発明と同様にＮを含むＴｉ−Ａｌ系合金も知られているが、Ａｌの溶融温度以下の低温焼結素材に過ぎない（非特許文献１，２）。
また、特許文献１では、Ａｌは焼結助剤として用いられているに過ぎず本願発明と異なる。
A Ti—Al alloy containing N is also known as in the present invention, but it is only a low-temperature sintered material having a melting temperature of Al or less (Non-Patent Documents 1 and 2).
Further, in Patent Document 1, Al is only used as a sintering aid and is different from the present invention.
本発明は、製造が容易であって（換言すれば製造コストが安く）、耐熱性を有する高強度で軽量なＴｉ−Ａｌ系合金を得る技術を提供することを目的とする。 An object of the present invention is to provide a technique for obtaining a high-strength and lightweight Ti—Al alloy having heat resistance, which is easy to manufacture (in other words, the manufacturing cost is low).
請求項１に係る発明は、それぞれ粉末状のＡｌ、ＴｉＮ、Ｔｉを重量比にてＡｌ：ＴｉＮ：Ｔｉ＝１：０．０１〜１．５：ｘ（ただし、ｘは０以上でありＴｉＮの比率との和が０．３以上６．０以下となる値）として混合し、真空または無酸素雰囲気下にてこの混合粉末を加圧しながら６６０℃〜１３５０℃で加熱して得ることを特徴とする耐熱軽量高強度焼結体製造方法である。
この範囲は、図５に示すＴｉ−Ａｌ−Ｎ系三元状態図の網掛け部となる。
なお、Ｏを不可避的不純物元素として、上限を３ｗｔ％として可能な限り低くするように制御ないし調整することが好ましい。
同様に、Ｐ，Ｓ，Ｓｉ，Ｍｎ，Ｓｎ，Ｚｎ，Ｆｅ，Ｎｉ，Ｃｏ，Ｃｕ，Ｍｏ，Ｗ，または，Ｈｆは含有元素として許容されるが、これらも上限を各３ｗｔ％、合計１０ｗｔ％として制御ないし調整することが好ましい。
In the invention according to claim 1, powdered Al, TiN, and Ti are divided by weight into Al: TiN: Ti = 1: 0.01 to 1.5: x (where x is 0 or more and TiN. The mixture is mixed as a sum of 0.3 or more and 6.0 or less), and the mixed powder is heated at 660 ° C to 1350 ° C while pressurizing in a vacuum or oxygen-free atmosphere. This is a method for producing a heat-resistant, lightweight, high-strength sintered body.
This range is the shaded portion of the Ti-Al-N system ternary phase diagram shown in FIG.
It is preferable to control or adjust O as an unavoidable impurity element with an upper limit of 3 wt% as low as possible.
Similarly, P, S, Si, Mn, Sn, Zn, Fe, Ni, Co, Cu, Mo, W, or Hf are allowed as contained elements, but these also have an upper limit of 3 wt% each, for a total of 10 wt%. It is preferable to control or adjust as.
混合するとは均一な状態に混ぜ合わせることをいう。
加熱とは、所定の昇温工程が含まれていてもよいものとする。加熱して焼結体をえる手段は特に限定されないが、ホットプレス、放電プラズマ焼結、ＨＩＰ（熱間等方加圧）を挙げることができる。
焼結体は合金と言い換えることもできる。
Ａｌ１に対し、ＴｉＮが０．０１を下回ると所期の添加効果がえられず、１．５を超えると窒化物量が増えすぎて靭性が低下し実用材料として適当でなくなる。同様に、Ｔｉとしての合計添加量が０．３に満たないと低融点層が生じて高温における機械的特性が不足し、６．０を超えると目的とするＴｉ−Ａｌ系化合物に対してＴｉ（α）量が増加し所期の特性が得られにくくなる。
Mixing means mixing in a uniform state.
The heating may include a predetermined temperature raising step. The means for obtaining the sintered body by heating is not particularly limited, and examples thereof include hot pressing, discharge plasma sintering, and HIP (hot isotropic pressurization).
The sintered body can be rephrased as an alloy.
If TiN is less than 0.01 with respect to Al1, the desired addition effect cannot be obtained, and if it exceeds 1.5, the amount of nitride increases too much and the toughness decreases, making it unsuitable as a practical material. Similarly, if the total amount of Ti added is less than 0.3, a low melting point layer is formed and the mechanical properties at high temperatures are insufficient. If it exceeds 6.0, Ti is obtained with respect to the target Ti—Al compound. The amount of (α) increases and it becomes difficult to obtain the desired characteristics.
請求項２に係る発明は、Ａｌ粉末の平均粒径を１μｍ以上１ｍｍ以下、および／または、ＴｉＮ粉末の平均粒径を５０μｍ以下とすることを特徴とする請求項１に記載の耐熱軽量高強度焼結体製造方法である。 The invention according to claim 2 is the heat-resistant, lightweight and high-strength according to claim 1, wherein the average particle size of the Al powder is 1 μm or more and 1 mm or less, and / or the average particle size of the TiN powder is 50 μm or less. This is a method for producing a sintered body.
Ａｌの平均粒径が１μｍを下回ると粉末表面積の増加により不純物元素である酸素量が過多となる。一方１ｍｍを超えると焼結時にＡｌと内部まで反応せずＴｉＡｌ３等の化合物の殻を生じて不均一組織となり、後の高温拡散時に空隙等の欠陥要因となる。また、ＴｉＮの平均粒径が５０μｍを超えると粗大なＴｉＮが未反応のまま残留しやすくなり、靭性等の機械的特性の低下を招く。 When the average particle size of Al is less than 1 μm, the amount of oxygen, which is an impurity element, becomes excessive due to the increase in the surface area of the powder. On the other hand, if it exceeds 1 mm, it does not react with Al to the inside at the time of sintering, and a shell of a compound such as TiAl 3 is formed to form a non-uniform structure, which causes defects such as voids at the time of subsequent high temperature diffusion. Further, when the average particle size of TiN exceeds 50 μm, coarse TiN tends to remain unreacted, which causes deterioration of mechanical properties such as toughness.
請求項３に係る発明は、Ｃｒ、Ｎｂ、Ｖ、Ｚｒ、Ｂを特性調整用元素とし、重量比でＡｌ１に対し、Ｃｒ粉末もしくはＣｒＮ粉末を０．５以下、Ｎｂ粉末もしくはＮｂＮ粉末を１．０以下、Ｖ粉末もしくはＶＮ粉末を０．３以下、Ｚｒ粉末もしくはＺｒＮ粉末を０．３以下、または、Ｂ粉末もしくはＢＮ粉末を０．１以下、添加した混合粉末を用いることを特徴とする請求項１または２に記載の耐熱軽量高強度焼結体製造方法である。 In the invention according to claim 3, Cr, Nb, V, Zr, and B are used as characteristic adjusting elements, Cr powder or CrN powder is 0.5 or less, and Nb powder or NbN powder is 1. A claim characterized in that a mixed powder containing 0 or less, V powder or VN powder of 0.3 or less, Zr powder or ZrN powder of 0.3 or less, or B powder or BN powder of 0.1 or less is used. Item 2. The method for producing a heat-resistant, lightweight, high-strength sintered body according to Item 1 or 2.
なお、窒化物すなわち、ＣｒＮ（本願ではＣｒＮと表記する際にはＣｒ２Ｎを含むものとする）、ＮｂＮ、ＶＮ、ＺｒＮまたはＢＮを添加する場合には、請求項１に関しては、Ａｌ：ＴｉＮ＋ＣｒＮ＋ＮｂＮ＋ＶＮ＋ＺｒＮ＋ＢＮ＝１：０．００１〜１．０となるように、ＴｉＮの添加量を調整する。 Incidentally, nitride i.e., (assumed to include a Cr 2 N is when expressed as CrN in this application) CrN, NbN, VN, in the case of adding ZrN or BN is, for claim 1, Al: TiN + CrN + NbN + VN + ZrN + BN = 1 The amount of TiN added is adjusted so as to be 0.001 to 1.0.
請求項４に係る発明は、特性調整用元素として添加する粉末の平均粒径を１００μｍ以下とすることを特徴とする請求項３記載の耐熱軽量高強度焼結体製造方法である。 The invention according to claim 4 is the method for producing a heat-resistant, lightweight, high-strength sintered body according to claim 3, wherein the average particle size of the powder added as an element for adjusting the characteristics is 100 μm or less.
請求項５に係る発明は、加熱に際し、加圧しながら６６０〜１０００℃の範囲にて加熱する第一工程を経た後、１０００〜１３５０℃の範囲にて拡散熱処理を施す第二工程を経ることを特徴とする請求項１〜４のいずれか一つに記載の耐熱軽量高強度焼結体製造方法である。 The invention according to claim 5 is to undergo a first step of heating in the range of 660 to 1000 ° C. while pressurizing, and then a second step of performing diffusion heat treatment in the range of 1000 to 1350 ° C. The heat-resistant, lightweight, high-strength sintered body manufacturing method according to any one of claims 1 to 4.
請求項６に係る発明は、第一工程と第二工程との間に、鍛造、切削その他の整形工程を含ませることを特徴とする請求項５に記載の耐熱軽量高強度焼結体製造方法である。 The method for producing a heat-resistant, lightweight, high-strength sintered body according to claim 5, wherein the invention according to claim 6 includes a forging, cutting, or other shaping step between the first step and the second step. Is.
請求項７に係る発明は、加熱温度を１１００〜１３５０℃として、圧延、鍛造、押出しその他の熱間加工工程を含ませることを特徴とする請求項１〜４のいずれか一つに記載の耐熱軽量高強度焼結体製造方法である。 The heat resistance according to any one of claims 1 to 4, wherein the invention according to claim 7 has a heating temperature of 1100 to 1350 ° C. and includes rolling, forging, extrusion and other hot working steps. This is a method for producing a lightweight and high-strength sintered body.
請求項８に係る発明は、Ａｌの融点を含み６８０℃までの反応温度領域における圧力より、前記反応温度を超えた温度領域における圧力を高めた加圧とすることを特徴とする請求項１〜７のいずれか一つに記載の耐熱軽量高強度焼結体製造方法である。 The invention according to claim 8 is characterized in that the pressure is increased in the temperature region exceeding the reaction temperature from the pressure in the reaction temperature region up to 680 ° C. including the melting point of Al. The method for producing a heat-resistant, lightweight, high-strength sintered body according to any one of 7.
反応温度領域とは、Ａｌの融点である６６０℃を下回り、Ａｌ粉とＴｉ粉との接触界面にてＡｌ−Ｔｉ合金が形成されはじめる温度（条件にも依存するが６００℃程度以上）から６８０℃までをいう。
圧力の目安は、反応温度領域では５ＭＰａ〜２０ＭＰａ、反応温度を超えてからは３０ＭＰａ〜１００ＭＰａの例を挙げることができる。
The reaction temperature region is below the melting point of Al, 660 ° C, and is 680 from the temperature at which the Al—Ti alloy begins to form at the contact interface between the Al powder and the Ti powder (depending on the conditions, about 600 ° C or higher). Up to ℃.
As a guideline of the pressure, an example of 5 MPa to 20 MPa in the reaction temperature range and 30 MPa to 100 MPa after the reaction temperature is exceeded can be given.
本発明によれば、耐熱性を有する高強度で軽量なＴｉ−Ａｌ−Ｎ系合金を、容易に製造ないし安価に製造することができる。 According to the present invention, a high-strength and lightweight Ti—Al—N-based alloy having heat resistance can be easily or inexpensively produced.
Ａｌ−Ｔｉの二元合金を製造する際には、Ａｌが融解すると、型の隙間から流れ出てしまい、Ａｌ融点を超えた温度での焼結は積極的に検討されてこなかった経緯がある。
加えて、融点を若干下回る温度にて、Ａｌ粉とＴｉ粉との接触界面でＡｌ−Ｔｉ合金が形成され、これが強固な殻となりその後の効率的な反応が進みにくいという側面がある。場合により、殻の中に空隙が残存してしまうこともある。いずれにせよ、Ａｌ融点付近以上の焼結ないし合金形成に関しては、ミクロな組成の不均一性が解消されにくく、機械的特性が期待されるほど発揮されない。
When producing a binary alloy of Al—Ti, when Al melts, it flows out from the gap of the mold, and sintering at a temperature exceeding the melting point of Al has not been positively studied.
In addition, at a temperature slightly below the melting point, an Al—Ti alloy is formed at the contact interface between the Al powder and the Ti powder, which forms a strong shell, which makes it difficult for the subsequent efficient reaction to proceed. In some cases, voids may remain in the shell. In any case, with respect to sintering or alloy formation above the Al melting point, it is difficult to eliminate the non-uniformity of the microcomposition, and the mechanical properties are not exhibited as expected.
本願発明者らは鋭意検討の結果、従来ＴｉＮ粉末はこれまで比較的安定な化合物としてしか認識されていなかったところ、これにＡｌに対する反応焼結原料としての有用性を発見し本発明をなしたものでる。
具体的には、本願発明者らは、ＴｉＮ粉末を混和して加熱すると、Ａｌの溶融とほぼ同時にＴｉＮが反応して融点上昇を導き、型からの漏れ出しが事実上生じず、また、Ａｌ融点以上の高温域における安定した加圧焼結および拡散処理が可能となることを発見した。
また、ＡｌとＴｉＮとの混合原料に、Ｔｉ粉末が存在していても、ＴｉＮ粉末の存在下では、同様の原理で反応が好適に進行することも確認した。
これらの知見をもとに、以下、本発明の実施例を説明する。
As a result of diligent studies, the inventors of the present application have made the present invention by discovering the usefulness of TiN powder as a reaction sintering raw material for Al, which has been conventionally recognized only as a relatively stable compound. It's a thing.
Specifically, when the TiN powder is mixed and heated, the inventors of the present application react with TiN almost at the same time as the melting of Al, leading to an increase in the melting point, and virtually no leakage from the mold occurs, and Al It was discovered that stable pressure sintering and diffusion treatment are possible in the high temperature range above the melting point.
It was also confirmed that even if Ti powder is present in the mixed raw material of Al and TiN, the reaction proceeds favorably in the presence of TiN powder by the same principle.
Based on these findings, examples of the present invention will be described below.
≪実施例１≫
平均粒径約１００μｍのＡｌ粉末１に対し、平均粒径約０．８μｍのＴｉＮ粉末を０．６７の重量割合で混合した後、黒鉛型を使用した放電プラズマ焼結（ＳＰＳ）を行ない、組織観察、硬さ試験、抗折試験を行なって特性を確認した。
＜ＳＰＳの条件＞
・加圧条件：初期加圧１０ＭＰａ，８００℃到達時以降５０ＭＰａ
・加熱条件：ＲＴ〜６００℃［３０℃／分］→６００℃〜８００℃［１０℃／分］→８００℃×３０分保持→８００℃〜１０５０℃［１０℃／分］→１０５０℃〜１１００℃［２．５℃／分］→１１００℃×６０分保持→その後冷却
<< Example 1 >>
TiN powder having an average particle size of about 0.8 μm was mixed with Al powder 1 having an average particle size of about 100 μm at a weight ratio of 0.67, and then discharge plasma sintering (SPS) using a graphite mold was performed to obtain a structure. The characteristics were confirmed by observing, hardness test, and bending test.
<SPS conditions>
・ Pressurization conditions: Initial pressurization 10 MPa, 50 MPa after reaching 800 ° C
-Heating conditions: RT to 600 ° C [30 ° C / min] → 600 ° C to 800 ° C [10 ° C / min] → 800 ° C x 30 minutes holding → 800 ° C to 1050 ° C [10 ° C / min] → 1050 ° C to 1100 ℃ [2.5 ℃ / min] → 1100 ℃ × 60 minutes holding → then cooling
＜組織観察＞
光学顕微鏡写真を図１に示した。写真から明らかなように、十分均質であるまではいえず、空隙も見られる。これは、原料粉末の粒子サイズの差が大きく、また、拡散処理温度が低めだったためと考えられた。また、Ａｌ自体の粒径が大きい影響とも考えられた。
なお、細かく観察したところ、ＡｌをベースとするＦＣＣ（面心立方格子構造）相、Ａｌ３Ｔｉ相、および、Ａｌ２Ｔｉ相がマトリックスを構成し、Ｔｉ（Ａｌ）Ｎ複合窒化物が析出する形となっていた。
<Tissue observation>
An optical micrograph is shown in FIG. As is clear from the photograph, it is not sufficiently homogeneous, and voids can be seen. It was considered that this was because the difference in particle size of the raw material powder was large and the diffusion treatment temperature was low. It was also considered that the particle size of Al itself was large.
Upon close observation, the FCC (face-centered cubic lattice structure) phase based on Al, the Al 3 Ti phase, and the Al 2 Ti phase form a matrix, and Ti (Al) N composite nitride is precipitated. It was in shape.
＜硬さ＞
微小硬さ分布は７５７ＨＶ０．５〜９４６ＨＶ０．５であり、平均値は８３６ＨＶ０．５であった。この値は実用鉄合金の最高硬さ（粉末ハイスの熱処理最高硬さ）に匹敵するレベルであり、高硬度素材であることが確認できた。
<Hardness>
The micro-hardness distribution was 757 HV0.5 to 946 HV0.5, and the average value was 836 HV0.5. This value is at a level comparable to the maximum hardness of a practical iron alloy (the maximum heat treatment hardness of powdered ferroalloy), and it was confirmed that it is a high hardness material.
＜抗折試験＞
次に、比抗折強度測定をおこなった。
まず、抗折試験をおこない、その結果を表１に示す。
Next, the specific bending strength was measured.
First, a folding test was performed, and the results are shown in Table 1.
本試験材（試験材１）の比重は３．７ｇ／ｃｍ３であった（軽合金といえる）。
従って、比抗折強度は次のとおりである。
常温：９７ＭＰａ／（Ｍｇ／ｍ３）、
１０００℃：８６ＭＰａ／（Ｍｇ／ｍ３）
この値は、実用特性として、軽量でありながら鉄合金の最高硬さに匹敵し、耐熱強度も備えているといえる。従って、軽量耐熱耐摩耗材として広い用途に有望な素材であることが確認できた。
The specific gravity of this test material (test material 1) was 3.7 g / cm 3 (it can be said to be a light alloy).
Therefore, the specific bending strength is as follows.
Room temperature: 97MPa / (Mg / m 3 ),
1000 ° C: 86 MPa / (Mg / m 3 )
As a practical characteristic, this value is comparable to the maximum hardness of iron alloys while being lightweight, and it can be said that it also has heat resistance. Therefore, it was confirmed that it is a promising material for a wide range of applications as a lightweight heat-resistant and abrasion-resistant material.
≪実施例２≫
平均粒径約７５μｍのＡｌ粉末１に対し、平均粒径約０．８μｍ粒径のＴｉＮ粉末を０．６５、平均粒径約４０μｍのＴｉ粉末を１．８の重量割合として混合し、更に、平均粒径約５μｍのＣｒＮ粉末を０．０３加えてよく混合した後、黒鉛型を使用した放電プラズマ焼結（ＳＰＳ）を行ない、組織観察、硬さ試験、抗折試験を行って特性を確認した。
＜ＳＰＳの条件＞
・加圧条件：初期加圧１０ＭＰａ，８００℃到達時以降５０ＭＰａ
・加熱条件：ＲＴ〜６００℃［３０℃／分］→６００℃〜８００℃［１０℃／分］→８００℃×３０分保持→８００℃〜１１５０℃［１０℃／分］→１１５０〜１２００℃［２．５℃／分］→１２００℃×６０分保持→その後冷却
<< Example 2 >>
TiN powder having an average particle size of about 0.8 μm was mixed with an Al powder 1 having an average particle size of about 75 μm as a weight ratio of 0.65, and Ti powder having an average particle size of about 40 μm was mixed as a weight ratio of 1.8. After adding 0.03 of CrN powder with an average particle size of about 5 μm and mixing well, discharge plasma sintering (SPS) using a graphite mold is performed, and structure observation, hardness test, and bending test are performed to confirm the characteristics. did.
<SPS conditions>
・ Pressurization conditions: Initial pressurization 10 MPa, 50 MPa after reaching 800 ° C
-Heating conditions: RT to 600 ° C [30 ° C / min] → 600 ° C to 800 ° C [10 ° C / min] → 800 ° C x 30 minutes holding → 800 ° C to 1150 ° C [10 ° C / min] → 1150 to 1200 ° C [2.5 ° C / min] → 1200 ° C x 60 minutes holding → then cooling
＜組織観察＞
光学顕微鏡写真を図２に示した。写真から明らかなように、５０μｍ径程度以下の未固溶ＴｉＮ粒子が若干確認されるものの、大部分はＴｉＡｌ（微量のＣｒを含む）とＴｉ３Ａｌを主体とするマトリックスであり、これに、個々には識別できない微細（１μｍオーダー）なＴｉ２ＡｌＮが析出した状態となっていた。全体として橙色を帯びた比較的均質な組織が形成されているといえる。
<Tissue observation>
An optical micrograph is shown in FIG. As it is evident from the photograph, although 50μm diameter of about less undissolved TiN particles is confirmed slightly, the majority is a matrix mainly composed of Ti 3 Al and TiAl (including Cr traces), in which, Fine particles (on the order of 1 μm) that could not be individually identified were precipitated in Ti 2 AlN. It can be said that a relatively homogeneous structure with an orange tinge is formed as a whole.
＜硬さ＞
微少硬さ分布は４２０ＨＶ０．５〜５４０ＨＶ０．５であり、平均値は４６６ＨＶ０．５であった。この値は、焼入れ焼戻しを施した鉄鋼の硬さに相当する。
<Hardness>
The fine hardness distribution was 420HV0.5 to 540HV0.5, and the average value was 466HV0.5. This value corresponds to the hardness of hardened and tempered steel.
＜抗折試験＞
次に、比抗折強度測定をおこなった。
まず、抗折試験をおこない、その結果を表２に示す。
Next, the specific bending strength was measured.
First, a folding test was conducted, and the results are shown in Table 2.
本試験材（試験材２）の比重は４．０３ｇ／ｃｍ３であった（軽合金といえる）。
従って、比抗折強度は次のとおりである。
常温：１４６ＭＰａ／（Ｍｇ／ｍ３）、
１０００℃：１１８ＭＰａ／（Ｍｇ／ｍ３）
図３に、各種耐熱合金における温度と比強度との関係を示した。１０００℃における試験材２の比抗折強度は、図示した従来得られているＴｉＡｌ二元合金の最高値と同等以上であるといえる。
The specific gravity of this test material (test material 2) was 4.03 g / cm 3 (it can be said to be a light alloy).
Therefore, the specific bending strength is as follows.
Room temperature: 146 MPa / (Mg / m 3 ),
1000 ° C: 118 MPa / (Mg / m 3 )
FIG. 3 shows the relationship between the temperature and the specific strength of various heat-resistant alloys. It can be said that the specific bending strength of the test material 2 at 1000 ° C. is equal to or higher than the maximum value of the conventionally obtained TiAl binary alloy shown in the figure.
≪比較例≫
次に、比較例として、Ｔｉ−４８ａｔ％Ａｌ合金（二元合金）を説明する。
平均粒径約７５μｍ粒径のＡｌ粉末１に対し、平均粒径約４０μｍのＴｉ粉末を０．５の重量割合で混合した後、黒鉛型を使用した放電プラズマ焼結（ＳＰＳ）を行ない、組織観察、硬さ試験をおこなった。
を確認した。焼結条件は実施例２と同じとした。
≪Comparison example≫
Next, as a comparative example, a Ti-48 at% Al alloy (binary alloy) will be described.
Ti powder with an average particle size of about 40 μm is mixed with Al powder 1 having an average particle size of about 75 μm at a weight ratio of 0.5, and then discharge plasma sintering (SPS) using a graphite mold is performed to obtain a structure. Observation and hardness test were conducted.
It was confirmed. The sintering conditions were the same as in Example 2.
＜組織観察＞
光学顕微鏡写真を図４に示した。一見うまく焼結されているように見えるが詳細に観察したところ、原料のＡｌ粒がほぼそのままとなっており（Ａｌ富化部として残存し）、外殻の化合物領域に覆われた、均質化の不十分なミクロ組織が形成されていることを確認した。
<Tissue observation>
An optical micrograph is shown in FIG. At first glance, it seems that it is sintered well, but when observed in detail, the Al grains of the raw material remain almost as they are (remaining as an Al enriched part), and the homogenization is covered with the compound region of the outer shell. It was confirmed that an inadequate microstructure was formed.
＜硬さ＞
ビッカース硬さ試験を実施した結果、２３４ＨＶ０．５〜４８０ＨＶ０．５であり、平均値は２８５ＨＶ０．５であった。実施例１，２と比較すると硬さは低く、局所的な硬化層が存在してばらつきも大きい。すなわち、本発明（実施例）の方が、均質であり、高硬度であるといえる。
<Hardness>
As a result of carrying out the Vickers hardness test, it was 234HV0.5 to 480HV0.5, and the average value was 285HV0.5. Compared with Examples 1 and 2, the hardness is low, a locally hardened layer is present, and the variation is large. That is, it can be said that the present invention (Example) is more homogeneous and has higher hardness.
以上の実施例および比較例から、本発明の方法は、従来のＴｉＡｌ合金における特殊な溶解鋳造法によることなく、低コストな製造方法であるといえる。また、得られる合金は、取扱性に優れ均質であって、従来品より高硬度かつ１０００℃程度の高温域において同等以上の比強度を有するものである。 From the above Examples and Comparative Examples, it can be said that the method of the present invention is a low-cost manufacturing method without using a special melt casting method for a conventional TiAl alloy. Further, the obtained alloy has excellent handleability and is homogeneous, has a higher hardness than the conventional product, and has a specific strength equal to or higher than that in a high temperature range of about 1000 ° C.
なお、本発明の温度域等について補足する。
図５は、Ａｌ−Ｔｉ−Ｎの三元状態図である。本発明の製造方法における原料の組成範囲は、図中の（１）〜（５）で示した黒丸印（５箇所）を頂点とする五角形内である。なお、図では実施例と比較例の組成点も記している。
The temperature range and the like of the present invention will be supplemented.
FIG. 5 is a ternary phase diagram of Al—Ti—N. The composition range of the raw material in the production method of the present invention is within a pentagon having the black circles (5 points) shown by (1) to (5) in the figure as vertices. In the figure, the composition points of Examples and Comparative Examples are also shown.
焼結体を製造する際の焼結温度ないし熱拡散温度は、６６０℃〜１３５０℃である。６６０℃はＡｌの融点であり、１３５０℃はＴｉ−Ａｌ−Ｎ三元状態図上で液相を生じうる温度である（後述）。 The sintering temperature or heat diffusion temperature at the time of producing the sintered body is 660 ° C. to 1350 ° C. 660 ° C. is the melting point of Al, and 1350 ° C. is the temperature at which a liquid phase can be formed on the Ti—Al—N ternary phase diagram (described later).
反応焼結原料としてＴｉの全部または一部をＴｉＮで代替することにより、焼結性向上が認められるが、ＣｒＮを添加使用した場合にもその効果が認められ、このほか、Ｃｒ単体、もしくは、Ｎｂ、Ｖ、Ｚｒ、Ｂまたはこれらの窒化物でも同等の効果がみとめられる。この現象は、概略的に言えば、ＴｉとＡｌとの化合物のみからなる粉末の外殻構造を生成する反応に対し、窒素の存在によりＡｌＮなどの微細な窒化物生成反応が加わることによって焼結温度が高温化し、Ａｌ融点付近での焼結反応を生ずるため、最終製品の均一性が得られやすくなると解釈される。 By substituting TiN for all or part of Ti as the reaction sintering raw material, the sinterability is improved, but the effect is also recognized when CrN is added and used. In addition, Cr alone or Cr alone or Equivalent effects can be seen with Nb, V, Zr, B or nitrides thereof. Roughly speaking, this phenomenon is sintered by the addition of a fine nitride formation reaction such as AlN due to the presence of nitrogen to the reaction of forming a powder outer shell structure consisting only of a compound of Ti and Al. It is interpreted that the uniformity of the final product can be easily obtained because the temperature rises and a sintering reaction occurs near the melting point of Al.
また、このような窒化物を原料に使用すると、製品の強度も向上する。先に示した様に、従来のＴｉＡｌ（代表組成として４８ａｔ％Ａｌ−５２ａｔ％Ｔｉ）合金では、約２５０ＨＶ程度のところ、Ｔｉの重量分率で約１／３をＴｉＮで置換えると、焼結まま製品で約４５０ＨＶ−５００ＨＶとなり、圧縮強度に換算すると２倍強のレベルとなる。 Further, when such a nitride is used as a raw material, the strength of the product is also improved. As shown above, in the conventional TiAl (48at% Al-52at% Ti as a representative composition) alloy, when about 250HV is replaced with about 1/3 of the weight fraction of Ti with TiN, it is sintered. As it is, the product will be about 450HV-500HV, which is more than double the compression strength.
更に、窒化物を原料に使用すると、耐熱性、即ち熱間強度と耐酸化性が向上する。マトリックスを形成するＴｉ−Ａｌ系化合物相のみならず窒化チタン及び合金窒化物の添加で生じる窒素化合物（ＡｌＮ、Ｔｉ２ＡｌＮや準安定相として存在しうるＴｉＮなど）は、従来の熱力学データからいずれも１３５０℃以上まで極めて安定な層であると考えられる。マトリックスのγＴｉＡｌ相などへ侵入窒素による固溶強化と微細窒化物の析出強化の効果をもたらし、同時に耐酸化性も向上させることが確認される。 Further, when a nitride is used as a raw material, heat resistance, that is, hot strength and oxidation resistance are improved. Not only the Ti—Al compound phase forming the matrix, but also the nitrogen compounds (AlN, Ti2AlN, TiN that can exist as a metastable phase, etc.) generated by the addition of titanium nitride and alloy nitride are all from the conventional thermodynamic data. It is considered that the layer is extremely stable up to 1350 ° C. or higher. It is confirmed that the effect of solid solution strengthening by invading nitrogen into the γTiAl phase of the matrix and the precipitation strengthening of fine nitrides is brought about, and at the same time, the oxidation resistance is also improved.
なお、図６および図７に、Ｔｈｒｍｏ−Ｃａｌｃ（サーモカルクソフトウェア社によるソフトウェア）による計算例を示した。本発明により得られる合金は周辺の領域において、ＴｉＡｌ、Ｔｉ３Ａｌ、ＴｉＡｌ３、ＡｌＮ、Ｔｉ２ＡｌＮ及び平衡しうるマトリックスのＡｌベースのＦＣＣ相、Ｔｉ（α）ベースのＨＣＰ相、更に準安定相として若干量残留しうると考えられるＴｉＮまで含め、主要な構成相が全て約１３５０℃まで安定と考えられる。但し、現実の製品はアルミニウム粉末の表面に形成される酸化相による５ｍａｓｓ％以下の酸素混入があるなどの要因で、一定の誤差を生じうる。 In addition, FIG. 6 and FIG. 7 show a calculation example by Thrmo-Calc (software by Thermocalc Software Co., Ltd.). The alloys obtained by the present invention have TiAl, Ti 3 Al, TiAl 3 , AlN, Ti 2 AlN and an equilibrium matrix Al-based FCC phase, Ti (α) -based HCP phase, and metastable in the surrounding regions. It is considered that all the main constituent phases are stable up to about 1350 ° C., including TiN, which is considered to be able to remain in a small amount as a phase. However, in an actual product, a certain error may occur due to factors such as oxygen contamination of 5 mass% or less due to the oxidation phase formed on the surface of the aluminum powder.
次に、二段階の焼結工程について説明する。第一段階の焼結工程は６６０℃〜１０００℃の所定温度における所定時間の保持であり、第二段階の焼結工程は１０００℃（場合によっては１１００℃）〜１３５０℃の所定温度における所定時間の保持である。
１０００℃以下の短時間加圧焼結では原料粒子サイズに起因する不均一性が残存し、合金化と硬化が十分でない部分が存在しうるため、この段階での焼結体は、目標となる耐熱強度を有するに至っていない。しかしながら、中間体として切削加工や塑性加工を行なうには有利な場合もある。従って、中間体を加工してから拡散処理を行なうのが製品の成形に有利な場合がある。もっとも、第一段階（低温側）の焼結後、そのまま冷却せずに第二段階（高温側）の焼結すなわち、拡散加圧焼結に移行してもよい。
Next, the two-step sintering process will be described. The first-stage sintering step is holding at a predetermined temperature of 660 ° C. to 1000 ° C. for a predetermined time, and the second-stage sintering step is a predetermined time at a predetermined temperature of 1000 ° C. (1100 ° C.) to 1350 ° C. Is the retention of.
In the short-time pressure sintering at 1000 ° C. or lower, non-uniformity due to the raw material particle size remains, and there may be a portion where alloying and curing are not sufficient. Therefore, the sintered body at this stage is a target. It does not have heat resistance. However, it may be advantageous to perform cutting or plastic working as an intermediate. Therefore, it may be advantageous for molding the product to process the intermediate and then perform the diffusion treatment. However, after the first stage (low temperature side) sintering, the second stage (high temperature side) sintering, that is, diffusion pressure sintering may be performed without cooling as it is.
拡散処理、或いは高温側での加圧焼結の目的は、Ｔｉ−Ａｌ−Ｎ系耐熱化合物、即ちＴｉＡｌ、Ｔｉ３Ａｌ，Ｔｉ２ＡｌＮ，ＡｌＮ等の耐熱平衡相の析出による耐熱性の付与と高強度化及び均質化の実現である。Ｔｉ−Ａｌ−Ｎ系では１０００℃程度を境にして平衡する高温相と低温相の種類が若干変わる傾向があるので、約１０００℃以上で保持することが有効である。但し、１３５０℃を超えると液相が生じる危険性があり、拡散処理は１０００〜１３５０℃の範囲とする。 The purpose of diffusion treatment or pressure sintering on the high temperature side is to impart heat resistance by precipitating heat-resistant equilibrium phases such as Ti—Al—N heat-resistant compounds, that is, TiAl, Ti 3 Al, Ti 2 AlN, and AlN. Achievement of high strength and homogenization. In the Ti—Al—N system, the types of the high temperature phase and the low temperature phase that equilibrate at about 1000 ° C. tend to change slightly, so it is effective to keep the temperature at about 1000 ° C. or higher. However, if the temperature exceeds 1350 ° C, there is a risk of a liquid phase being formed, and the diffusion treatment is in the range of 1000 to 1350 ° C.
仕様の態様によっては、１１００℃以上の高温領域で熱間鍛造や熱間圧延といった塑性加工が行われうる。この場合も材温が１３５０℃を超えると液相が生じまた組織が粗大化するため、熱間鍛造や熱間圧延は１１００〜１３５０℃の温度範囲で行なうことが望ましい。 Depending on the aspect of the specifications, plastic working such as hot forging or hot rolling can be performed in a high temperature region of 1100 ° C. or higher. In this case as well, if the material temperature exceeds 1350 ° C., a liquid phase is formed and the structure becomes coarse. Therefore, it is desirable to perform hot forging and hot rolling in the temperature range of 1100 to 1350 ° C.
次に、特性調整用元素について説明する。Ｃｒ、Ｎｂ、Ｖ、Ｚｒ、Ｂは、Ｔｉ−Ａｌ合金に添加すると、酸化性と高温での組織安定性を向上させることが可能であり、これら、または、これらの窒化物を本発明の方法によるＡｌ−Ｔｉ−Ｎ系合金の製造に際し添加すれば、同様の効果が得られるほか、焼結初期にＴｉＮ粉末と同様のＡｌとの反応性を利用できる（焼結性の調整が可能となる）。 Next, the element for adjusting the characteristics will be described. When Cr, Nb, V, Zr, and B are added to the Ti—Al alloy, it is possible to improve the oxidizing property and the structure stability at high temperature, and these or these nitrides can be used in the method of the present invention. If it is added in the production of an Al—Ti—N alloy according to the above, the same effect can be obtained, and the same reactivity with Al as the TiN powder can be utilized at the initial stage of sintering (the sinterability can be adjusted). ).
Ｃｒの場合は、上述の成形性向上効果が顕著であり、耐酸化性向上効果もあるが、多すぎると低融点化合物を生成しやすくなるため、Ａｌの重量１に対してＣｒ又はＣｒＮを０．５以下とする。
Ｎｂは耐酸化性効果が大きいが、多すぎると比重を大きくし、粗大窒化物を作り好ましくないのでＡｌの重量１に対してＮｂ又はＮｂＮを１．０以下とする。
Ｚｒ，Ｖについては耐酸化性及び熱間強度向上の効果が認められるが、多すぎると比重を大きくし、また粗大窒化物を作り好ましくないのでＡｌの重量１に対してＺｒ又はＺｒＮ、Ｖ又はＶＮとも０．３以下とする。
Ｂについては微量で組織の安定化効果、熱間強度向上効果が認められるが、多すぎると粗大窒化物を作り好ましくないのでＡｌの重量１に対してＢ又はＢＮ０．１以下とする。
In the case of Cr, the above-mentioned effect of improving moldability is remarkable, and there is also an effect of improving oxidation resistance. However, if the amount is too large, a low melting point compound is likely to be produced. Therefore, Cr or CrN is set to 0 with respect to 1 weight of Al. It shall be 5.5 or less.
Nb has a large oxidation resistance effect, but if it is too large, the specific gravity is increased and it is not preferable to form a coarse nitride. Therefore, Nb or NbN is set to 1.0 or less with respect to 1 weight of Al.
Regarding Zr and V, the effects of improving oxidation resistance and hot strength are recognized, but if it is too much, the specific gravity will be increased and coarse nitrides will be formed, which is not preferable. Therefore, Zr or ZrN, V or Both VN shall be 0.3 or less.
A small amount of B has a structure stabilizing effect and a hot strength improving effect, but if it is too large, coarse nitrides are formed, which is not preferable. Therefore, B or BN is 0.1 or less with respect to 1 weight of Al.
なお、これら、特性調整用元素粉末（窒化物を含む）の平均粒径は、１００μｍ以下とするのが好ましい。１００μｍを超えると、その元素の拡散に時間がかかり、製品のミクロ組織が不均質となって、所期の各種特性が得られにくくなるからである The average particle size of these element powders for adjusting characteristics (including nitrides) is preferably 100 μm or less. This is because if it exceeds 100 μm, it takes time to diffuse the element, the microstructure of the product becomes inhomogeneous, and it becomes difficult to obtain various desired characteristics.
Ｏ（酸素）は微細粉末を使用するのである程度の混入は不可避であるが、多くなりすぎると材料の脆化が顕著となるので最終製品（合金）の組成において３ｗｔ％以下で且つ極力低減する必要がある。 Since fine powder is used for O (oxygen), it is unavoidable to mix it to some extent, but if it is too large, the material becomes embrittled, so it is necessary to reduce the composition of the final product (alloy) to 3 wt% or less as much as possible. There is.
また、Ｐ，Ｓ，Ｓｉ，Ｍｎ，Ｓｎ，Ｚｎ，Ｆｅ，Ｎｉ，Ｃｏ，Ｃｕ，Ａｇ，Ｍｏ，Ｗ，Ｈｆは、本発明に見られる合金の基本的な作用機序を成立させる範囲で許容されうる。上記の各元素について、０．５ｗｔ％のレベルで顕著な有害性は確認されない。個別の上限として３ｗｔ％、合計で１０ｗｔ％を超える場合には本発明合金の基本特性が維持されにくい。従って、最終製品の組成として、個別に３ｗｔ％以下、合計で１０ｗｔ％以下の範囲で混入または添加する。 Further, P, S, Si, Mn, Sn, Zn, Fe, Ni, Co, Cu, Ag, Mo, W and Hf are allowed as long as the basic mechanism of action of the alloy found in the present invention is established. Can be done. No significant toxicity has been identified at the 0.5 wt% level for each of the above elements. When the individual upper limit exceeds 3 wt%, and the total exceeds 10 wt%, it is difficult to maintain the basic characteristics of the alloy of the present invention. Therefore, the composition of the final product is individually mixed or added in the range of 3 wt% or less, that is, 10 wt% or less in total.
本発明によれば、従来の航空機エンジン部品のほか、高温環境下で強度が要求されるおよび／または軽量であることが要求される構造材を安価に提供できる。 According to the present invention, in addition to conventional aircraft engine parts, structural materials that are required to be strong and / or lightweight in a high temperature environment can be provided at low cost.
Claims (8)
真空または無酸素雰囲気下にてこの混合粉末を加圧しながら６６０℃〜１３５０℃で加熱して得ることを特徴とする耐熱軽量高強度焼結体製造方法。 Powdered Al, TiN, and Ti in weight ratio of Al: TiN: Ti = 1: 0.01 to 1.5: x (where x is 0 or more and the sum with the TiN ratio is 0.3. Mix as (a value that is greater than or equal to 6.0 or less).
A method for producing a heat-resistant, lightweight, high-strength sintered body, which is obtained by heating the mixed powder at 660 ° C. to 1350 ° C. while pressurizing it in a vacuum or an oxygen-free atmosphere.
重量比でＡｌ１に対し、
Ｃｒ粉末もしくはＣｒＮ粉末を０．５以下、
Ｎｂ粉末もしくはＮｂＮ粉末を１．０以下、
Ｖ粉末もしくはＶＮ粉末を０．３以下、
Ｚｒ粉末もしくはＺｒＮ粉末を０．３以下、または、
Ｂ粉末もしくはＢＮ粉末を０．１以下、
添加した混合粉末を用いることを特徴とする請求項１または２に記載の耐熱軽量高強度焼結体製造方法。 Cr, Nb, V, Zr, B are used as the element for adjusting the characteristics.
By weight ratio to Al1
Cr powder or CrN powder 0.5 or less,
Nb powder or NbN powder 1.0 or less,
V powder or VN powder 0.3 or less,
Zr powder or ZrN powder 0.3 or less, or
B powder or BN powder 0.1 or less,
The method for producing a heat-resistant, lightweight, high-strength sintered body according to claim 1 or 2, wherein the added mixed powder is used.
加圧しながら６６０〜１０００℃の範囲にて加熱する第一工程を経た後、
１０００〜１３５０℃の範囲にて拡散熱処理を施す第二工程を経ることを特徴とする請求項１〜４のいずれか一つに記載の耐熱軽量高強度焼結体製造方法。 When heating
After going through the first step of heating in the range of 660 to 1000 ° C while pressurizing,
The method for producing a heat-resistant, lightweight, high-strength sintered body according to any one of claims 1 to 4, wherein the second step of performing diffusion heat treatment in the range of 1000 to 1350 ° C. is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019051005A JP7334896B2 (en) | 2019-03-19 | 2019-03-19 | Heat-resistant, lightweight, high-strength sintered body manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019051005A JP7334896B2 (en) | 2019-03-19 | 2019-03-19 | Heat-resistant, lightweight, high-strength sintered body manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2020152945A true JP2020152945A (en) | 2020-09-24 |
| JP7334896B2 JP7334896B2 (en) | 2023-08-29 |
Family
ID=72557902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019051005A Active JP7334896B2 (en) | 2019-03-19 | 2019-03-19 | Heat-resistant, lightweight, high-strength sintered body manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7334896B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342421A (en) * | 2020-10-20 | 2021-02-09 | 长安大学 | Vanadium nitride multi-field coupling preparation process and device |
| WO2022260026A1 (en) * | 2021-06-09 | 2022-12-15 | 株式会社Ihi | Tial alloy, tial alloy powder, tial alloy component, and method for producing same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49104807A (en) * | 1973-02-09 | 1974-10-03 | ||
| JPH02200743A (en) * | 1989-01-30 | 1990-08-09 | Sumitomo Light Metal Ind Ltd | Method for compacting ti-al series intermetallic compound member |
| JPH08225879A (en) * | 1995-02-15 | 1996-09-03 | Agency Of Ind Science & Technol | Titanium nitrode sintered compact using aluminum as auxiliary and its production |
| JPH11172351A (en) * | 1997-12-12 | 1999-06-29 | Agency Of Ind Science & Technol | Ti-al alloy, production of the alloy, and method for joining the alloy |
| CN1944338A (en) * | 2006-10-24 | 2007-04-11 | 武汉理工大学 | Synthesizing dense titanium aluminum nitride-titanium nitride composite block material by in site thermal press process |
| CN103846438A (en) * | 2014-02-20 | 2014-06-11 | 福州阿石创光电子材料有限公司 | Method for manufacturing TiAlN metal ceramic composite target |
-
2019
- 2019-03-19 JP JP2019051005A patent/JP7334896B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49104807A (en) * | 1973-02-09 | 1974-10-03 | ||
| JPH02200743A (en) * | 1989-01-30 | 1990-08-09 | Sumitomo Light Metal Ind Ltd | Method for compacting ti-al series intermetallic compound member |
| JPH08225879A (en) * | 1995-02-15 | 1996-09-03 | Agency Of Ind Science & Technol | Titanium nitrode sintered compact using aluminum as auxiliary and its production |
| JPH11172351A (en) * | 1997-12-12 | 1999-06-29 | Agency Of Ind Science & Technol | Ti-al alloy, production of the alloy, and method for joining the alloy |
| CN1944338A (en) * | 2006-10-24 | 2007-04-11 | 武汉理工大学 | Synthesizing dense titanium aluminum nitride-titanium nitride composite block material by in site thermal press process |
| CN103846438A (en) * | 2014-02-20 | 2014-06-11 | 福州阿石创光电子材料有限公司 | Method for manufacturing TiAlN metal ceramic composite target |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342421A (en) * | 2020-10-20 | 2021-02-09 | 长安大学 | Vanadium nitride multi-field coupling preparation process and device |
| WO2022260026A1 (en) * | 2021-06-09 | 2022-12-15 | 株式会社Ihi | Tial alloy, tial alloy powder, tial alloy component, and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7334896B2 (en) | 2023-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6261618B2 (en) | Method for producing titanium material and nitrogen solid solution titanium powder material | |
| Bolzoni et al. | Quantifying the properties of low-cost powder metallurgy titanium alloys | |
| CN109848420B (en) | 440C stainless steel metal powder injection molding method and product thereof | |
| ES2698523T3 (en) | Procedure to produce a construction element from a composite material with a metallic matrix and intermetallic phases incorporated | |
| KR20190143164A (en) | High entropy alloys with intermetallic compound precipitates for strengthening and method for manufacturing the same | |
| WO2013047511A1 (en) | Fe-based powder-densely-solidified molding having excellent high-temperature strength | |
| JP2010532822A (en) | Titanium aluminide alloy manufacturing method, titanium aluminide alloy structural material manufacturing method, and titanium aluminide alloy structural material | |
| JP7334896B2 (en) | Heat-resistant, lightweight, high-strength sintered body manufacturing method | |
| WO2013162658A2 (en) | Oxygen-enriched ti-6ai-4v alloy and process for manufacture | |
| JP5759426B2 (en) | Titanium alloy and manufacturing method thereof | |
| JP6011946B2 (en) | Nickel-based intermetallic compound composite sintered material and method for producing the same | |
| JP2021121690A (en) | TiAl-BASED ALLOY AND MANUFACTURING METHOD THEREOF | |
| US5000910A (en) | Method of manufacturing intermetallic compound | |
| US20160207110A1 (en) | Corrosion resistant article and methods of making | |
| JP2014169471A (en) | Ni-BASED INTERMETALLIC COMPOUND SINTERED BODY, AND PRODUCING METHOD THEREFOR | |
| JP6667264B2 (en) | Manufacturing method of high-rigidity iron-based sintered alloy | |
| KR102429733B1 (en) | Corrosion resistant article and methods of making | |
| JPH04325648A (en) | Production of sintered aluminum alloy | |
| CN109311086B (en) | Method for producing titanium or titanium alloy components by powder metallurgy | |
| JP2004143596A (en) | Tenacious metallic nano-crystalline bulk material with high hardness and high strength, and its manufacturing method | |
| Zhang et al. | The sintering densification, microstructure and mechanical properties of Ti–48Al–2Cr–2Nb by a small addition of Sn–Al powder | |
| WO2020032235A1 (en) | NITRIDE-DISPERSED MOLDED BODY WHICH IS FORMED OF Ni-BASED ALLOY | |
| JP2019014920A (en) | Co-BASED ALLOY POWDER FOR ELECTRON BEAM LAMINATION MOLDING | |
| WO2017077923A1 (en) | Nitrogen-solid-soluted titanium sintered compact and method for producing same | |
| CN113597476B (en) | Method for manufacturing Co-based alloy structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220310 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230111 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230207 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20230406 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230518 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230711 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230808 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7334896 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |