JP4353617B2 - Corrosion-resistant and wear-resistant Ni alloys and parts for plastic kneaders and molding machines - Google Patents
Corrosion-resistant and wear-resistant Ni alloys and parts for plastic kneaders and molding machines Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、プラスチック混練機又は成形機の部材として使用される耐食耐摩耗性に優れたＮｉ合金および該合金からなる混練機・成形機用部材に関する。
【０００２】
【従来の技術】
プラスチック成形技術分野では、樹脂組成物の混練機，成形機を構成する部材の耐食性の改善が強く要請されている。例えば、ふっ素樹脂は耐熱性，耐薬品性等に優れることから需要が増大しているが、その樹脂組成物の混練／成形の際に弗化水素酸を含む腐食性成分を発生するため、機器の腐食損傷が大きな問題となり、また燐酸等を含む樹脂組成物の混練／成形を行なう機器部材には、優れた耐食性を要求されることが多くなっている。
【０００３】
従来、プラスチックの混練機・成形機の構成部材、例えばシリンダ、スクリュー、ノズル等の部材料として、「ハステロイＣ」合金(Cr:16,Mo:
16,W: 4,Ni:Bal）、「インコネル６２５」合金（Cr:20,Mo:10,Nb:4,Ni:Bal）、
「コルモノイ♯５」合金（Cr:11.5,Fe:4.25,Si:3.75,B:2.5,C:0.65,Ni:Bal）、
「コルモノイ♯６」合金（Cr:13.5,Fe:4.75,Si:4.25,B:3.0,C:0.75,Ni:Bal）等のＮｉ合金が使用されている（元素含有量はいずれも重量％）。
【０００４】
【発明が解決しようとする課題】
上記合金は耐食性・耐摩耗性等の特性に一長一短を有する。「ハステロイＣ」合金、「インコネル６２５」合金は、卓抜した耐食性を有するものの、耐摩耗性に乏しく、特にセラミックス・ファイバー等の硬質物質を配合された樹脂組成物の混練・成形操業では、機材の摩耗損傷が進み易い。他方「コルモノイ♯５,♯６」等の合金は、耐摩耗性に優れてはいるが、耐食性に問題があり、腐食環境に対する信頼性に乏しい。
本発明は上記に鑑み、プラスチックの混練機・成形機等の構成部材料として改良された耐食性及び耐摩耗性を具備するＮｉ合金および該合金からなる部材を提供するものである。
【０００５】
【課題を解決するための手段】
本発明のＮｉ合金は、Ｍｏ：１０〜３０％、Ｗ ：１０〜３０％の１種又は２種（ＭｏとＭｏの複合含有の場合は合計量１０〜３０％）、Ｃｒ：２０〜５０％、Ｓｉ：０.２〜０.５重量％を含有し、残部はＮｉ及び不可避不純物からなる化学組成を有している。
【０００６】
本発明のＮｉ合金は、所望により、下記（ａ）〜（ｃ）項の１又は複数項から選択される１種ないし２種以上の元素でＮｉの一部を置換することにより、前記諸元素と共にこれら元素を含有する化学組成が与えられる。
（ａ）Ｃｕ，Ａｇ，Ａｕから選ばれる１種又は２種以上の元素：３〜１０重量％（２種以上の場合は合計量）、（ｂ）周期表第ＩＶＢ族、第ＶＢ族から選ばれる１種又は２種以上の元素：３〜２０重量％（２種以上の場合は合計量）、（ｃ）Ｆｅ：１０重量％以下。
【０００７】
本発明合金の成分限定理由は次のとおりである。元素含有量「％」は重量％である。
Ｍｏ：１０〜３０％
Ｍｏは基地中に固溶して合金の耐食性、特にハロゲン系等の非酸化性酸に対する腐食抵抗性を高める。またＭｏの一部はＮｉと結合し金属間化合物（Ｎｉ７Ｍｏ６等）を生成することによりマトリックスの耐摩耗性を高める。これらの効果を得るために１０％以上の添加を要する。増量により効果を増す。好ましくは１５％以上である。しかし、３０％を越えると耐食性の効果はほぼ飽和し、また強度の低下を生じるので、これを上限とする。
【０００８】
Ｗ：１０〜３０％
Ｗは、Ｍｏと同じように基地中に固溶して合金の耐食性を高める。特に、ハロゲン系等の非酸化性酸に対する腐食抵抗性の向上に有効である。またＷの一部はＮｉとの金属間化合物（Ｗ７Ｍｏ６等）を形成しマトリックスの耐摩耗性にも寄与する。これらの効果は１０％以上の添加により得られ、増量に伴って効果を増す。好ましくは１５％以上である。しかし、３０％を越えると、耐食性の改善効果が飽和するのみならず、強度の低下を生じるので、これを上限とする。
【０００９】
上記ＭｏとＷの２元素は択一的又は複合的に添加される。複合含有の場合は、その合計量を１０〜３０％の範囲とする。合計量が１０％に満たないと、特性改善効果が不足し、他方３０％を越えても効果の増加はなく、却って強度低下をきたすからである。
【００１０】
Ｃｒ：２０〜５０％
Ｃｒは、基地に固溶して合金の耐酸化性を高めると共に、耐食性、特に酸化性酸（硝酸等）に対する腐食抵抗性を高め、かつ固溶強化によるマトリックスの耐摩耗性の向上に奏効する。これらの効果は２０％以上の添加により得られる。増量に伴って効果を増すが、５０％を越えると、強度の低下を招くので、これを超えてはならない。
【００１１】
Ｃｕ，Ａｇ，Ａｕ：３〜１０％
Ｃｕ，Ａｇ，Ａｕ（第ＩＢ族）の各元素は、前記Ｍｏ又は／及びＷと共に添加されることにより、合金の耐食性、特にハロゲン系等の非酸化性酸に対する耐食性を高める効果を有する。添加量（２種以上の複合添加の場合は合計量）を３〜１０％の範囲に規定しているのは、これに満たないと添加効果が不足し、またこれを超えて多量に添加すると効果はほぼ飽和し経済性を損なうからである。
【００１２】
Ｓｉ：０．２〜５％
Ｓｉは合金溶製工程における脱酸剤として働き、また合金溶湯の流動性の向上に奏効する。合金溶湯の流動性は、鋳造合金の製造に必要な鋳造性を維持し、また焼結合金として製造する場合の焼結原料粉末を作製するためのアトマイズ処理性を維持するのに必要である。このために０．２％以上の添加を必要とする。しかし過度の増量は、耐食性、強度の低下を招くので５％を上限とする。
【００１３】
第ＩＶＢ族，第ＶＢ族元素：３〜２０％
第ＩＶＢ族（Ｔｉ，Ｚｒ，Ｈｆ）、第ＶＢ族（Ｖ，Ｎｂ，Ｔａ）の各元素は、合金の耐食性の向上に寄与する。前記Ｍｏ，Ｗ，Ｃｒ等の元素と共存することにより、３％程度の少量の添加でその効果を得ることができる。増量により合金の耐食性は増強されるが、強度の低下を伴い、また高価な元素であるので、２０％を上限とする。
【００１４】
Ｆｅ：１０％以下
Ｆｅは本発明合金の物性改善に寄与する元素ではなく、合金溶製時にＣｒ，Ｍｏ，Ｗ，Ｎｉ等を、鉄化合物Ｆｅ−Ｍ（ＭはＣｒ，Ｍｏ，Ｗ，Ｎｉ等）として添加する場合に持ち込まれる成分である。Ｃｒ，Ｍｏ，Ｗ，Ｎｉ等の比較的高価な元素を多量に含有する本発明合金の製造において、比較的安価に入手し得る鉄化合物Ｆｅ−Ｍを利用することは、合金コストの削減に有効である。ただし、Ｆｅの増量に伴って合金の耐食性を減じるので、１０％を上限として混在を許容することとした。
【００１５】
【発明の実施の形態】
本発明のＮｉ合金および該合金を適用されるプラスチック混練機・成形機の構成部材（シリンダー，スクリュー，ノズル等）は焼結合金（焼結体）として製造される。特に、熱間静水圧加圧成形（ＨＩＰ）法により形成される焼結体は、緻密・均質であり、本発明合金の物性を効果的に発揮させるのに有利である。同法によれば、スクリュー，ノズルなどの複雑形状部材をニアー・ネット・シェイプに製作することも容易である。ＨＩＰ処理は、１１００〜１２５０℃、１００ＭＰａ以上の加熱・加圧（保持時間は約１Ｈｒ以上）の条件下に、焼結反応の過不足をきたすことなく首尾良く達成され、高品質の焼結体を得ることができる。
【００１６】
本発明の合金を適用して形成される部材は、必ずしもその全肉厚を本発明の合金とする必要はない。部材の形態・使用態様に応じた適宜の構造用鋼を母材とし、その表面の全体もしくは耐食耐摩耗性を要する領域の表面に、本発明合金をライニングした積層構造とすることができる。例えば、シリンダーの場合はその母材円筒体の内周面に、スクリュー（シャフトとその周面を螺回する羽根とを有する）では、その母材の羽根部の表層（所望により羽根部の表層と併せてスクリューシャフトの周面）に、またノズルでは射出孔の内周面に、それぞれ本発明合金の焼結体からなるライニングを積層形成した構造が与えられる。
【００１７】
母材表面を被覆保護する上記ライニング層は、母材の所要領域の表面にカプセル材を介して本発明合金の粉末を装填しＨＩＰ処理することにより形成される。ＨＩＰ焼結体として形成されるライニング層は緻密・均質であると共に、母材表面に対し拡散結合により強固に密着し、母材保護層として優れた安定性を有する。ライニング層厚は１〜１０ｍｍ程度であればよい。
【００１８】
【実施例】
(1)供試材の作製
Ｎｉ合金粉末を焼結原料としてＨＩＰによる焼結体を得る。
ＨＩＰ処理：１２００℃×１１０ＭＰａ×２Ｈｒ。
【００１９】
(2)材料特性の評価
(2.1)耐食性
試験片を腐食試験液に浸漬し、試験後の腐食減量を測定する。
▲１▼弗化水素酸腐食試験
試験液：弗化水素酸溶液（濃度１０％），液温５０℃
試験時間：４８Ｈｒ
▲２▼燐酸腐食試験
試験液：燐酸溶液（濃度５０％），液温５０℃
試験時間：４８Ｈｒ
【００２０】
(2.2)摩耗試験
大越式迅速摩耗試験機による摩耗減量を測定し耐摩耗性を評価する。
相手材（回転輪）：軸受鋼SUJ-２（硬度HRC:60）
周速度：１．０９ｍ／秒
試験距離：４００ｍ
最終荷重：６２Ｎ
【００２１】
(2.3)曲げ試験
三点曲げ法による。
試験片：サイズ３×４，スパン距離３０ｍｍ
【００２２】
表１および表２に各供試材の合金組成および試験結果を示す。
比較例No.３２〜３７は、発明例に類似した成分組成を有しているが、元素含有量（表中下線付記）が過多又は不足の例である。No.３８とNo.３９は従来合金（市販材）について、前記と同一の試験条件により得られた測定結果を示している（No.３８：ハステロイＣ合金、No.３９：コルモノイ♯５合金）。
【００２３】
【表１】
【表２】
比較例No.３８（ハステロイＣ合金）は良好な耐食性を有しているが、硬度が低く耐摩耗性に劣り、No.３９（コルモノイ♯５合金）は硬質・高耐摩耗性であるものの、耐食性に劣る。これに対し発明例のものは、耐食性及び耐摩耗性に優れ、従来材No.３８とNo.３９の欠点を相補完し両者の長所を兼備している。また、プラスチック混練機・成形機の構成部材等として必要な機械強度を備えている。なお、発明例に類似した組成を有する比較例No.３２〜３７において、No.３２,No.３４（Ｍｏ,Ｗ,Ｃｒ等不足）は耐摩耗性に劣り耐食性も乏しい。No.３３,No.３５（Ｍｏ,Ｗ,Ｃｒ等過多）は高耐摩耗性と高耐食性を備えているが、強度の不足が著しく構造部材料としての適性に欠けている。またNo.３６（Ｓｉ過多）は強度の不足をきたし、No.３７（Ｆｅ量過剰）は耐食性の不足をきたしている。
【００２６】
【発明の効果】
本発明のＮｉ合金は、耐食性と耐摩耗性を具備し、これらの材料特性を要求されるプラスチック混練機・成形機等の構成部品の形成材料として適用されることにより、苛酷な腐食・摩耗環境に対する部材の耐久性を高め、機器のメンテナンス軽減、操業効率の向上等の効果をもたらす。本発明合金は、上記の機器構成部材のほか、耐食性および耐摩耗性を要求される構造部材料として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a Ni alloy having excellent corrosion resistance and abrasion resistance used as a member of a plastic kneader or a molding machine, and a kneader / molding machine member made of the alloy.
[0002]
[Prior art]
In the field of plastic molding technology, there is a strong demand for improvement of the corrosion resistance of the members constituting the resin composition kneader and molding machine. For example, the demand for fluororesin is increasing due to its excellent heat resistance and chemical resistance, but it generates corrosive components including hydrofluoric acid when kneading / molding the resin composition. Corrosion damage is a major problem, and excellent corrosion resistance is often required for equipment members for kneading / molding a resin composition containing phosphoric acid or the like.
[0003]
Conventionally, “Hastelloy C” alloy (Cr: 16, Mo: as a material for components of plastic kneaders and molding machines, for example, cylinders, screws, nozzles, etc.
16, W: 4, Ni: Bal), "Inconel 625" alloy (Cr: 20, Mo: 10, Nb: 4, Ni: Bal),
"Colmonoy # 5" alloy (Cr: 11.5, Fe: 4.25, Si: 3.75, B: 2.5, C: 0.65, Ni: Bal),
Ni alloys such as “Kolmonoy # 6” alloy (Cr: 13.5, Fe: 4.75, Si: 4.25, B: 3.0, C: 0.75, Ni: Bal) are used (element content is all by weight) .
[0004]
[Problems to be solved by the invention]
The above alloys have advantages and disadvantages in characteristics such as corrosion resistance and wear resistance. Although “Hastelloy C” alloy and “Inconel 625” alloy have outstanding corrosion resistance, they have poor wear resistance. Wear damage is easy to progress. On the other hand, alloys such as “colmonoy # 5, # 6” are excellent in wear resistance, but have a problem in corrosion resistance and are not reliable in a corrosive environment.
In view of the above, the present invention provides a Ni alloy having improved corrosion resistance and wear resistance as a component material for plastic kneaders and molding machines, and a member made of the alloy.
[0005]
[Means for Solving the Problems]
The Ni alloy of the present invention has one or two types of Mo: 10 to 30%, W: 10 to 30% (total amount of 10 to 30% in the case of composite inclusion of Mo and Mo), Cr: 20 to 50% , Si: 0.2 to 0.5 containing wt%, the balance has a chemical composition consisting of N i and unavoidable impurities.
[0006]
The Ni alloy of the present invention can be obtained by substituting a part of Ni with one or more elements selected from one or more of the following items (a) to ( c ), if desired. And a chemical composition containing these elements.
(A) One or more elements selected from Cu, Ag, Au: 3 to 10% by weight (total amount in the case of two or more elements), ( b ) Selected from groups IVB and VB of the periodic table One or two or more elements: 3 to 20% by weight (total amount in the case of two or more elements), ( c ) Fe: 10% by weight or less.
[0007]
The reasons for limiting the components of the alloy of the present invention are as follows. The element content “%” is% by weight.
Mo: 10-30%
Mo dissolves in the matrix and enhances the corrosion resistance of the alloy, particularly the corrosion resistance against non-oxidizing acids such as halogens. Further, a part of Mo is combined with Ni to form an intermetallic compound (Ni 7 Mo 6 or the like), thereby increasing the wear resistance of the matrix. In order to obtain these effects, addition of 10% or more is required. Increase the effect. Preferably it is 15% or more. However, if it exceeds 30%, the effect of corrosion resistance is almost saturated and the strength is lowered, so this is the upper limit.
[0008]
W: 10-30%
W, like Mo, dissolves in the matrix and improves the corrosion resistance of the alloy. In particular, it is effective for improving the corrosion resistance against non-oxidizing acids such as halogens. A part of W forms an intermetallic compound with Ni (W 7 Mo 6 or the like) and contributes to the wear resistance of the matrix. These effects are obtained by addition of 10% or more, and the effects increase with an increase in the amount. Preferably it is 15% or more. However, if it exceeds 30%, not only the corrosion resistance improving effect is saturated but also the strength is lowered, so this is the upper limit.
[0009]
The two elements Mo and W are added alternatively or in combination. In the case of complex inclusion, the total amount is in the range of 10 to 30%. If the total amount is less than 10%, the effect of improving the characteristics is insufficient. On the other hand, if the total amount exceeds 30%, the effect does not increase and the strength is decreased.
[0010]
Cr: 20-50%
Cr dissolves in the base to increase the oxidation resistance of the alloy, and also improves the corrosion resistance, particularly the corrosion resistance against oxidizing acids (such as nitric acid), and improves the wear resistance of the matrix by solid solution strengthening. . These effects can be obtained by adding 20% or more. The effect increases with the increase, but if it exceeds 50%, the strength is reduced, so this should not be exceeded.
[0011]
Cu, Ag, Au: 3 to 10%
By adding each element of Cu, Ag, Au (Group IB) together with the Mo or / and W, there is an effect of improving the corrosion resistance of the alloy, in particular, the corrosion resistance against non-oxidizing acids such as halogens. The addition amount (the total amount in the case of two or more combined additions) is specified in the range of 3 to 10% because if the amount is less than this, the addition effect is insufficient, and if it is added in a large amount beyond this This is because the effect is almost saturated and the economy is impaired.
[0012]
Si: 0.2 to 5%
Si acts as a deoxidizer in the alloy melting process and is effective in improving the fluidity of the molten alloy. The fluidity of the molten alloy is necessary to maintain the castability necessary for the production of the cast alloy, and to maintain the atomization property for producing the sintered raw material powder when producing the sintered alloy. For this reason, addition of 0.2% or more is required. However, an excessive increase leads to a decrease in corrosion resistance and strength, so the upper limit is 5%.
[0013]
Group IVB, Group VB elements: 3-20%
Each element of Group IVB (Ti, Zr, Hf) and Group VB (V, Nb, Ta) contributes to improvement of the corrosion resistance of the alloy. By coexisting with elements such as Mo, W and Cr, the effect can be obtained with a small amount of addition of about 3%. Although the corrosion resistance of the alloy is enhanced by increasing the amount, it is accompanied by a decrease in strength and is an expensive element, so 20% is made the upper limit.
[0014]
Fe: 10% or less Fe is not an element that contributes to the improvement of the physical properties of the alloy of the present invention, but Cr, Mo, W, Ni, etc. are converted into an iron compound Fe-M (M is Cr, Mo, W, Ni, etc.) ) Is a component brought in when added as. In the production of the alloy of the present invention containing a large amount of relatively expensive elements such as Cr, Mo, W, and Ni, it is effective to reduce the alloy cost to use the iron compound Fe-M that can be obtained at a relatively low cost. It is. However, since the corrosion resistance of the alloy is reduced as the amount of Fe is increased, mixing is allowed up to 10%.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The Ni alloy of the present invention and the constituent members (cylinder, screw, nozzle, etc.) of the plastic kneader and molding machine to which the alloy is applied are manufactured as a sintered alloy (sintered body). In particular, the sintered body formed by the hot isostatic pressing (HIP) method is dense and homogeneous, which is advantageous for effectively exhibiting the physical properties of the alloy of the present invention. According to this method, it is also easy to manufacture a complicated shape member such as a screw or a nozzle in a near net shape. HIP treatment is successfully achieved under the conditions of 1100 to 1250 ° C. and heating and pressurization of 100 MPa or more (holding time is about 1 Hr or more) without causing excess or deficiency of the sintering reaction. Can be obtained.
[0016]
The member formed by applying the alloy of the present invention is not necessarily required to have the entire thickness as the alloy of the present invention. It is possible to obtain a laminated structure in which an alloy of the present invention is lined on the entire surface or the surface of a region requiring corrosion and wear resistance, using an appropriate structural steel according to the form and usage of the member as a base material. For example, in the case of a cylinder, on the inner peripheral surface of the base material cylinder, on the screw (having a shaft and a blade that spirals the peripheral surface), on the surface of the blade part of the base material (if desired, the surface layer of the blade part) In addition, a structure in which a lining made of a sintered body of the alloy of the present invention is laminated on the peripheral surface of the screw shaft and the inner peripheral surface of the injection hole in the nozzle is provided.
[0017]
The lining layer for covering and protecting the surface of the base material is formed by charging the surface of a required region of the base material with the powder of the alloy of the present invention via a capsule material and performing HIP treatment. The lining layer formed as a HIP sintered body is dense and homogeneous, and is firmly adhered to the surface of the base material by diffusion bonding, and has excellent stability as a base material protective layer. The lining layer thickness should just be about 1-10 mm.
[0018]
【Example】
(1) Preparation of test material A sintered body by HIP is obtained using Ni alloy powder as a sintering raw material.
HIP treatment: 1200 ° C. × 110 MPa × 2 Hr.
[0019]
(2) Evaluation of material properties
(2.1) Immerse the corrosion resistance test piece in the corrosion test solution and measure the corrosion weight loss after the test.
(1) Hydrofluoric acid corrosion test liquid: hydrofluoric acid solution (concentration 10%), liquid temperature 50 ° C
Test time: 48 hours
(2) Phosphoric acid corrosion test liquid: phosphoric acid solution (concentration 50%), liquid temperature 50 ° C
Test time: 48 hours
[0020]
(2.2) Wear test Evaluate wear resistance by measuring wear loss with the Ogoshi rapid wear tester.
Mating material (rotating ring): Bearing steel SUJ-2 (Hardness HRC: 60)
Peripheral speed: 1.09 m / sec Test distance: 400 m
Final load: 62N
[0021]
(2.3) Bending test According to the three-point bending method.
Test piece: Size 3 × 4, span distance 30mm
[0022]
Tables 1 and 2 show the alloy compositions and test results of the test materials.
Comparative Examples Nos. 32 to 37 are examples having a component composition similar to that of the invention example, but the element content (underlined in the table) is excessive or insufficient. No. 38 and No. 39 show the measurement results obtained for the conventional alloy (commercially available material) under the same test conditions as described above (No. 38: Hastelloy C alloy, No. 39: Colmonoy # 5 alloy). .
[0023]
[Table 1]
[Table 2]
Comparative Example No. 38 (Hastelloy C alloy) has good corrosion resistance, but its hardness is low and inferior in wear resistance, while No. 39 (Kolmonoy # 5 alloy) is hard and highly wear resistant. Inferior to corrosion resistance. On the other hand, the invention example is excellent in corrosion resistance and wear resistance, complements the disadvantages of the conventional materials No. 38 and No. 39, and combines the advantages of both. In addition, it has the necessary mechanical strength as a component for plastic kneaders and molding machines. In Comparative Examples Nos. 32 to 37 having compositions similar to the inventive examples, Nos. 32 and 34 (insufficient Mo, W, Cr, etc.) have poor wear resistance and poor corrosion resistance. No. 33, No. 35 (excessive Mo, W, Cr, etc.) have high wear resistance and high corrosion resistance, but lack of strength is remarkably lacking in suitability as a structural part material. No. 36 (excessive Si) has insufficient strength, and No. 37 (excess Fe amount) has insufficient corrosion resistance.
[0026]
【The invention's effect】
The Ni alloy of the present invention has corrosion resistance and wear resistance, and is applied as a forming material for components such as plastic kneaders and molding machines that require these material characteristics, thereby causing severe corrosion and wear environments. This improves the durability of the components, reduces the maintenance of the equipment, and improves the operation efficiency. The alloy of the present invention is useful as a structural part material that requires corrosion resistance and wear resistance in addition to the above-mentioned equipment constituent members.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000156443A JP4353617B2 (en) | 2000-05-26 | 2000-05-26 | Corrosion-resistant and wear-resistant Ni alloys and parts for plastic kneaders and molding machines |
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| JP2000156443A JP4353617B2 (en) | 2000-05-26 | 2000-05-26 | Corrosion-resistant and wear-resistant Ni alloys and parts for plastic kneaders and molding machines |
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| JP4353617B2 true JP4353617B2 (en) | 2009-10-28 |
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| JP2003211441A (en) * | 2002-01-17 | 2003-07-29 | Japan Steel Works Ltd:The | Molding processing apparatus |
| JP4953371B2 (en) * | 2007-04-27 | 2012-06-13 | 独立行政法人日本原子力研究開発機構 | Ni-based alloy excellent in nitric acid corrosion resistance and method for producing the same |
| JP6062283B2 (en) * | 2013-02-22 | 2017-01-18 | 三菱重工マシナリーテクノロジー株式会社 | Kneading machine |
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