JP2008274412A - HIGH Cr-HIGH TEMPERATURE CORROSION RESISTANT Ni BASE ALLOY, AND HIGH TEMPERATURE CORROSION RESISTANT MEMBER - Google Patents
HIGH Cr-HIGH TEMPERATURE CORROSION RESISTANT Ni BASE ALLOY, AND HIGH TEMPERATURE CORROSION RESISTANT MEMBER Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 107
- 238000005260 corrosion Methods 0.000 title claims abstract description 107
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 39
- 239000000956 alloy Substances 0.000 title claims abstract description 39
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 15
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 230000032683 aging Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000002699 waste material Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000009863 impact test Methods 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
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- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
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Abstract
Description
本発明は、都市ごみや産業廃棄物等の廃棄物の焼却処理を行う焼却処理設備における燃焼炉の熱交換器等の、高温腐食環境下で使用される炉内設置物を形成する材料として用いられる高Ｃｒ−耐高温腐食Ｎｉ基合金、および該高Ｃｒ−耐高温腐食Ｎｉ基合金によって形成された耐高温腐食部材に関するものである。 The present invention is used as a material for forming in-furnace installations used in a high temperature corrosive environment, such as a heat exchanger of a combustion furnace in an incineration processing facility for incineration of waste such as municipal waste and industrial waste. The present invention relates to a high Cr—high temperature corrosion resistant Ni-based alloy and a high temperature corrosion resistant member formed of the high Cr—high temperature corrosion resistant Ni base alloy.
都市ごみや産業廃棄物等の廃棄物の焼却処理を行う焼却処理設備には、前記廃棄物を熱分解させて熱分解ガスと熱分解残留物とを生成する熱分解ドラムを有する熱分解反応器と、前記熱分解ガスを高温燃焼させる燃焼炉とを備えたものがある。燃焼炉内には熱交換器等の炉内設置物が設置され、８５０℃〜１２００℃程度の高温排ガス雰囲気、且つ、腐食性のガス（ＨＣｌ、ＳＯｘ等）雰囲気に曝される。熱交換器によって排ガスより回収した熱は、前記熱分解反応容器の熱源として利用されている。このような炉内設置物を形成する材料には、該炉内の独特の高温腐食環境下で高い耐食性を発揮することが求められる。 A pyrolysis reactor having a pyrolysis drum that pyrolyzes the waste to produce pyrolysis gas and pyrolysis residue in an incineration treatment facility that incinerates waste such as municipal waste and industrial waste And a combustion furnace for burning the pyrolysis gas at a high temperature. A furnace installation such as a heat exchanger is installed in the combustion furnace and exposed to a high-temperature exhaust gas atmosphere of about 850 ° C. to 1200 ° C. and a corrosive gas (HCl, SOx, etc.) atmosphere. The heat recovered from the exhaust gas by the heat exchanger is used as a heat source for the pyrolysis reaction vessel. The material forming such an in-furnace installation is required to exhibit high corrosion resistance under a unique high temperature corrosion environment in the furnace.
高温腐食環境下で高い耐食性を示す材料として、ＮｉおよびＣｒを多く含有する耐高温腐食性合金が知られている。例えば、本出願人は本発明より先に、Ｃ：０．１８〜０．２８ｗｔ％、Ｓｉ：３．００〜６．００ｗｔ％、Ｍｎ：０．１０ｗｔ％以下、Ｐ：０．０１ｗｔ％以下、Ｓ：０．０１ｗｔ％以下、Ｃｒ：３０．０〜３５．０ｗｔ％、Ｎｉ：４５．０〜５０．０ｗｔ％、Ｍｏ：４．５〜５．５ｗｔ％を含有し、さらに実施レベルの実用性から高い耐性を損なわないで許される成分範囲として、Ｍｎ：１．０ｗｔ％以下、Ｐ：０．０４ｗｔ％、Ｓ：０．０４ｗｔ％以下を含有し、残部がＦｅおよび不可避的不純物からなる高ＣｒのＮｉ基合金（以下、高Ｃｒ−Ｎｉ基合金）を提案している（特許文献１）。
特許文献１の高Ｃｒ−Ｎｉ基合金を長時間にわたって６５０℃〜９５０℃程度の高温で保持すると、Ｃｒの含有量が高いことに加え、ＳｉおよびＭｏの含有量も高いことに起因するσ相の時効析出に伴う脆性および母相の耐食性の低下が問題となる場合があることが明らかとなった。また、燃焼炉内の排ガス温度は１２００℃程度の高温にまで達するため、更に高温の腐食環境下で耐食性を発揮する合金が求められている。 When the high Cr—Ni-based alloy of Patent Document 1 is held at a high temperature of about 650 ° C. to 950 ° C. for a long time, in addition to the high Cr content, the σ phase resulting from the high Si and Mo content It has been clarified that the brittleness associated with the aging precipitation and the deterioration of the corrosion resistance of the parent phase may be problematic. Further, since the exhaust gas temperature in the combustion furnace reaches a high temperature of about 1200 ° C., an alloy that exhibits corrosion resistance in a higher temperature corrosive environment is required.
本発明の目的は、従来よりも高温の腐食環境に対して優れた耐食性を発揮すると共に、該高温環境下において靭性の低下しにくい高Ｃｒ−耐高温腐食Ｎｉ基合金を提供することにある。 An object of the present invention is to provide a high Cr-high temperature corrosion-resistant Ni-based alloy that exhibits excellent corrosion resistance against a corrosive environment at a higher temperature than that of the prior art and is less susceptible to lowering toughness in the high-temperature environment.
前述の通り、従来（特許文献１）の高Ｃｒ−Ｎｉ基合金を６５０℃〜９５０℃程度の高温で長時間保持すると、Ｃｒ含有量の高さに加えてＳｉおよびＭｏの含有量も高いことに起因するσ相の時効析出が生じ、これに伴う靭性低下および母相の耐食性の低下が問題となる場合がある。 As described above, when a conventional high Cr—Ni base alloy is held at a high temperature of about 650 ° C. to 950 ° C. for a long time, the content of Si and Mo is high in addition to the high Cr content. In some cases, aging precipitation of the σ phase due to the occurrence of aging occurs, resulting in a decrease in toughness and a decrease in the corrosion resistance of the matrix.
ここで、Ｓｉは、材料表面に酸化皮膜を形成して耐高温腐食性を向上させる作用を奏する元素である。更に、Ｓｉは、耐高温腐食性向上に有効なＣｒ酸化皮膜の内側にＳｉＯ２保護皮膜の連続層を形成し、該Ｃｒ酸化皮膜を安定させる作用を奏する。したがって、高Ｃｒの合金においてＳｉの含有量を減少させると、該高Ｃｒによる耐高温腐食性の安定性を損なう虞がある。 Here, Si is an element that has an effect of improving the high temperature corrosion resistance by forming an oxide film on the surface of the material. Furthermore, Si forms the continuous layer of the SiO 2 protective film inside the Cr oxide film effective for improving the high temperature corrosion resistance, and has an effect of stabilizing the Cr oxide film. Therefore, if the Si content in the high Cr alloy is reduced, the high temperature corrosion resistance stability due to the high Cr may be impaired.
本発明は、高Ｃｒによる耐高温腐食性を確保するため、特許文献１で提案した高Ｃｒ−Ｎｉ基合金をベースとして、Ｍｏの含有量を減少させたものである。
具体的には、本発明の第１の態様に係る高Ｃｒ−耐高温腐食Ｎｉ基合金の発明は、Ｎｉ：４５〜５０ｗｔ％、Ｃｒ：３０〜３５ｗｔ％、Ｍｏ：０．５ｗｔ％以上４．５ｗｔ％未満、Ｓｉ：３．０ｗｔ％を超えて６．０ｗｔ％以下、Ｃ：０．１８〜０．２８ｗｔ％を含有し、残部がＦｅおよび不可避的不純物からなることを特徴とするものである。
In the present invention, in order to ensure high-temperature corrosion resistance due to high Cr, the Mo content is reduced based on the high Cr—Ni based alloy proposed in Patent Document 1.
Specifically, the invention of the high Cr—high temperature corrosion resistant Ni-based alloy according to the first aspect of the present invention is as follows: Ni: 45-50 wt%, Cr: 30-35 wt%, Mo: 0.5 wt% or more. Less than 5 wt%, Si: more than 3.0 wt% and not more than 6.0 wt%, C: 0.18 to 0.28 wt%, with the balance being Fe and inevitable impurities .
ここで、Ｍｏもその添加が耐食性の向上に有効な元素であるため、Ｍｏの含有量を減少させると耐高温腐食性が低下すると予想される。
本発明において、Ｍｏの含有量を減少させることによって、靭性および耐高温腐食性を向上させることができる理由を以下に説明する。
Here, since addition of Mo is also an element effective for improving corrosion resistance, it is expected that the high temperature corrosion resistance is lowered when the Mo content is decreased.
The reason why the toughness and the high temperature corrosion resistance can be improved by reducing the Mo content in the present invention will be described below.
すなわち、Ｍｏの含有量を減少させることによって、Ｍｏが助長するσ相の時効析出が抑えられ、該σ相の時効析出に伴う靭性低下の問題が改善されることに加え、結果として母相には耐食性の向上に有効な量のＭｏが多く含有されることとなり、従来よりも優れた耐高温腐食性を有する高Ｃｒ−耐高温腐食Ｎｉ基合金とすることが可能となるものである。 That is, by reducing the Mo content, the aging precipitation of the σ phase promoted by Mo is suppressed, and the problem of toughness reduction associated with the aging precipitation of the σ phase is improved. Contains a large amount of Mo effective for improving corrosion resistance, and can be a high Cr-high temperature corrosion resistant Ni-base alloy having high temperature corrosion resistance superior to that of the prior art.
Ｍｏの含有量を前記範囲に設定することによって、高ＣｒによるＣｒ酸化皮膜による耐食効果とＳｉによるＣｒ酸化皮膜の安定化作用とを確保したまま、σ相の時効析出に伴う靭性低下を抑え、ベース合金よりも優れた耐高温腐食性および靭性を発揮する高Ｃｒ−耐高温腐食Ｎｉ基合金とすることができる。 By setting the content of Mo in the above range, while suppressing the corrosion resistance effect due to the Cr oxide film due to high Cr and the stabilization effect of the Cr oxide film due to Si, toughness reduction due to aging precipitation of σ phase is suppressed, A high Cr-high temperature corrosion resistant Ni-based alloy that exhibits high temperature corrosion resistance and toughness superior to the base alloy can be obtained.
次に、各合金元素の含有率を上記の範囲に限定した理由について説明する。
（１）Ｎｉについて
Ｎｉは、母相の安定化、および耐高温腐食性の向上に有効な元素である。しかも、母相の靭性を向上させる作用があるため、廃棄物の焼却処理を行う焼却処理設備における燃焼炉等の炉内での加熱によりある程度の金属間化合物が析出しても十分な靭性が確保できるように、含有量の下限を４５ｗｔ％とした。一方、含有量が多くなると、耐サルファアタック性が低下するし、コストも高くなるので、上限を５０％とした。
Next, the reason why the content of each alloy element is limited to the above range will be described.
(1) About Ni Ni is an element effective for stabilizing the matrix phase and improving high-temperature corrosion resistance. In addition, because it has the effect of improving the toughness of the matrix phase, sufficient toughness is ensured even if some intermetallic compounds are precipitated by heating in a furnace such as a combustion furnace in an incineration facility that incinerates waste. In order to make it possible, the lower limit of the content was set to 45 wt%. On the other hand, when the content is increased, the resistance to sulfur attack is lowered and the cost is also increased. Therefore, the upper limit is set to 50%.
（２）Ｃｒについて
Ｃｒは、高温強度を向上させるのに有効なうえ、材料表面に酸化皮膜を形成して耐高温腐食性の向上に優れた効果を示す。本発明においては、９５０℃程度の高温の腐食環境下で十分な耐食性を得られるように、含有量の下限を３０ｗｔ％とした。しかし、過度に添加すると、σ相の時効析出を促進して靭性を低下させるうえ、Ｃｒ炭化物の析出を促進して耐食性をかえって低下させるので、上限を３５ｗｔ％とした。
(2) About Cr In addition to being effective in improving high temperature strength, Cr forms an oxide film on the surface of the material and exhibits an excellent effect in improving high temperature corrosion resistance. In the present invention, the lower limit of the content is set to 30 wt% so that sufficient corrosion resistance can be obtained in a high-temperature corrosive environment of about 950 ° C. However, if excessively added, the aging precipitation of the σ phase is promoted to lower toughness, and the precipitation of Cr carbide is promoted to reduce the corrosion resistance. Therefore, the upper limit is set to 35 wt%.
（３）Ｃについて
Ｃは、耐熱鋼として必要な高温強度および耐クリープ性を向上させるのに有効な元素であり、０．１８ｗｔ％以上含有することが好ましいが、含有量が多くなるとＣｒ炭化物の析出を促進して耐食性を低下させるため、含有量の上限は０．２８ｗｔ％とした。
(3) About C C is an element effective for improving the high-temperature strength and creep resistance necessary as a heat-resistant steel, and is preferably contained in an amount of 0.18 wt% or more. In order to promote precipitation and reduce corrosion resistance, the upper limit of the content was set to 0.28 wt%.
（４）Ｓｉについて
Ｓｉは、材料表面に酸化皮膜を形成して耐高温腐食性を向上させる作用が知られている。また、Ｓｉは、耐高温腐食性向上に有効なＣｒ酸化皮膜の内側にＳｉＯ２保護皮膜の連続層を形成し、該Ｃｒ酸化皮膜を安定させる作用を奏する。前記ＳｉＯ２保護皮膜の連続層を形成させるため、Ｓｉは３．０ｗｔ％を超えて含有されることが好ましい。一方、含有量が多くなるとσ相の時効析出を促進して材料の靭性を低下させるので、上限を６．０ｗｔ％とした。
(4) About Si It is known that Si forms an oxide film on the surface of the material to improve the high temperature corrosion resistance. In addition, Si forms the continuous layer of the SiO 2 protective film inside the Cr oxide film effective for improving the high temperature corrosion resistance, and has an effect of stabilizing the Cr oxide film. In order to form a continuous layer of the SiO 2 protective film, Si is preferably contained in an amount exceeding 3.0 wt%. On the other hand, as the content increases, the aging precipitation of the σ phase is promoted and the toughness of the material is lowered, so the upper limit was made 6.0 wt%.
（５）Ｍｏについて
Ｍｏも、耐高温腐食性向上に有効な元素である。特に、Ｃｒ含有量が高い場合には、Ｃｒの濃縮したδ相が腐食の起点となる。前記δ相の腐食を抑制するため、Ｍｏは０．５ｗｔ％以上含有することが好ましい。一方、過度に添加するとσ相の時効析出を助長する。Ｍｏが助長するσ相の時効析出による母相の耐食性の低下を抑え、９５０℃程度の高温での耐食性を確保するため、上限は４．５ｗｔ％未満とした。
(5) About Mo Mo is also an element effective for improving high-temperature corrosion resistance. In particular, when the Cr content is high, the δ phase enriched with Cr becomes a starting point of corrosion. In order to suppress corrosion of the δ phase, Mo is preferably contained in an amount of 0.5 wt% or more. On the other hand, excessive addition promotes aging precipitation of the σ phase. In order to suppress the deterioration of the corrosion resistance of the matrix due to the aging precipitation of the σ phase promoted by Mo and to ensure the corrosion resistance at a high temperature of about 950 ° C., the upper limit was made less than 4.5 wt%.
本発明の第２の態様に係る耐高温腐食部材は、高Ｃｒ−耐高温腐食Ｎｉ基合金によって構成されている高温腐食環境下で使用される高靭性耐高温腐食部材であって、前記高Ｃｒ−耐高温腐食Ｎｉ基合金は、Ｎｉ：４５〜５０ｗｔ％、Ｃｒ：３０〜３５ｗｔ％、Ｍｏ：０．５ｗｔ％以上４．５ｗｔ％未満、Ｓｉ：３．０ｗｔ％を超えて６．０ｗｔ％以下、Ｃ：０．１８〜０．２８ｗｔ％を含有し、残部がＦｅおよび不可避的不純物からなることを特徴とするものである。本発明によれば、第１の態様と同様の作用効果を奏する耐高温腐食部材とすることができる。 The high temperature corrosion resistant member according to the second aspect of the present invention is a high toughness high temperature corrosion resistant member used in a high temperature corrosion environment composed of a high Cr-high temperature corrosion resistant Ni-based alloy, -High temperature corrosion resistant Ni-base alloy is Ni: 45-50 wt%, Cr: 30-35 wt%, Mo: 0.5 wt% or more and less than 4.5 wt%, Si: more than 3.0 wt% and 6.0 wt% or less , C: 0.18 to 0.28 wt%, with the balance being Fe and inevitable impurities. According to this invention, it can be set as the high temperature corrosion-resistant member which has the effect similar to a 1st aspect.
本発明によれば、Ｃｒ含有量が高いことによる耐高温腐食性を確保したまま、σ相の時効析出に伴う靭性の低下も抑えることが可能となり、優れた耐高温腐食性および靭性を発揮する高Ｃｒ−耐高温腐食Ｎｉ基合金とすることができる。 According to the present invention, it is possible to suppress a decrease in toughness due to aging precipitation of the σ phase while ensuring high-temperature corrosion resistance due to high Cr content, and exhibit excellent high-temperature corrosion resistance and toughness. It can be a high Cr-high temperature corrosion resistant Ni-base alloy.
本発明に係る高Ｃｒ−耐高温腐食Ｎｉ基合金である実施例１〜実施例６の化学組成（実施例２、３、５および６は分析値、実施例１および３は目標値である）を表１に示す。
実施例１〜実施例６の高Ｃｒ−耐高温腐食Ｎｉ基合金に対し、後述する高温腐食試験（耐高温腐食性評価）を行った。また、高温腐食試験後の試験片に対して腐食界面の分析を行った。なお、実施例１〜実施例６の比較例として、表１に示す比較例１〜比較例３の化学組成（分析値）の合金についても、高温腐食試験および耐高温腐食試験後の腐食界面の分析を行った。なお、比較例１は、特許文献１に記載された高Ｃｒ−Ｎｉ基合金である。
更に、実施例２、実施例６、および比較例１について、シャルピー衝撃試験（靭性評価）を行った。
Chemical compositions of Examples 1 to 6 which are high Cr-high temperature corrosion resistant Ni-based alloys according to the present invention (Examples 2, 3, 5 and 6 are analytical values, and Examples 1 and 3 are target values) Is shown in Table 1.
The high Cr-high temperature corrosion resistant Ni-based alloys of Examples 1 to 6 were subjected to a high temperature corrosion test (high temperature corrosion resistance evaluation) described later. Moreover, the corrosion interface was analyzed with respect to the test piece after a high temperature corrosion test. In addition, as a comparative example of Examples 1 to 6, the alloys having chemical compositions (analytical values) of Comparative Examples 1 to 3 shown in Table 1 also have a corrosion interface after the high temperature corrosion test and the high temperature corrosion resistance test. Analysis was carried out. Comparative Example 1 is a high Cr—Ni based alloy described in Patent Document 1.
Further, Charpy impact test (toughness evaluation) was performed on Example 2, Example 6, and Comparative Example 1.
《高温腐食試験：耐高温腐食性評価方法》
ＪＩＳ Ｚ２２９３「金属材料の塩浸漬及び塩埋没高温腐食試験法」に一部準じ、灰組成などについて改変した下記の条件の高温腐食試験を試験片について行った。該高温腐食試験を実施した後の試験片の脱スケールは、３％過マンガン酸カリウム＋５％水酸化ナトリウム水溶液と、５％クエン酸アンモニウム水溶液中で交互に煮沸することによって行った。脱スケール後、試薬塗布面積当たりの重量減少を算出し、この腐食減量（ｍｇ／ｃｍ２）をもって耐高温腐食性評価の指標とした。前記高温腐食試験の条件を以下に示す。
[High-temperature corrosion test: Evaluation method for high-temperature corrosion resistance]
In accordance with JIS Z2293 “Salt immersion and salt immersion high temperature corrosion test method of metal material”, a high temperature corrosion test under the following conditions modified for ash composition and the like was performed on the test piece. The descaling of the test piece after the hot corrosion test was carried out was performed by alternately boiling in 3% potassium permanganate + 5% aqueous sodium hydroxide and 5% aqueous ammonium citrate. After descaling, the weight loss per area where the reagent was applied was calculated, and this weight loss (mg / cm 2 ) was used as an index for evaluating high temperature corrosion resistance. The conditions of the high temperature corrosion test are shown below.
＜高温腐食試験条件＞
試験片形状／寸法： 板材／１０ｍｍ×１０ｍｍ×２ｍｍ
灰条件： Al2O3-NaCl-KCl-Na2SO4-K2SO4混合試薬（重量比60：9：6：15：10）中に
３ｍｍの深さに埋没
試験温度／保持時間／雰囲気： ９５０℃／２００ｈ／大気中
<High temperature corrosion test conditions>
Test piece shape / dimensions: Plate material / 10 mm × 10 mm × 2 mm
Ash condition: Al 2 O 3 -NaCl-KCl-Na 2 SO 4 -K 2 SO 4 in mixed reagent (weight ratio 60: 9: 6: 15: 10)
Buried in a depth of 3 mm Test temperature / holding time / atmosphere: 950 ° C./200 h / in air
《腐食界面観察および分析》
前記高温腐食試験後の試験片表面に対し、腐食界面付近の断面を鏡面研磨し、ＳＥＭによる観察およびＥＰＭＡによる相分析を行った。
<< Corrosion interface observation and analysis >>
A cross section near the corrosion interface was mirror-polished on the surface of the test piece after the high temperature corrosion test, and observation by SEM and phase analysis by EPMA were performed.
《シャルピー衝撃試験：靭性評価方法》
ＪＩＳ Ｚ２２４２「金属材料のシャルピー衝撃試験方法」に準じ、大気中で、各々６５０℃／１７０ｈ、７５０℃／１７０ｈ、８５０℃／１７０ｈで時効した試験片を幅が７．５ｍｍのサブサイズＶノッチ試験片に加工し、室温にてシャルピー衝撃試験を行った。
《Charpy impact test: toughness evaluation method》
In accordance with JIS Z2242 “Charpy impact test method for metal materials”, test pieces aged at 650 ° C./170 h, 750 ° C./170 h, and 850 ° C./170 h, respectively, in the atmosphere are sub-size V-notch tests with a width of 7.5 mm. The piece was processed and subjected to a Charpy impact test at room temperature.
表２に高温腐食試験後の各試験片の腐食減量の測定値、およびシャルピー衝撃試験による衝撃値の測定値を示す。また、図１は高温腐食試験結果を示すグラフである。 Table 2 shows the measured value of corrosion weight loss of each test piece after the high temperature corrosion test and the measured value of the impact value by the Charpy impact test. FIG. 1 is a graph showing the results of the high temperature corrosion test.
図１および表２に示されるように、実施例１〜実施例６の高Ｃｒ−耐高温腐食Ｎｉ基合金の９５０℃の腐食条件下における腐食減量（ｍｇ／ｃｍ２）は、比較例の１０分の１〜５分の１程度に抑えられており、優れた耐高温腐食性を有していると言える。 As shown in FIG. 1 and Table 2, the weight loss (mg / cm 2 ) of the high Cr—high temperature corrosion resistant Ni-based alloys of Examples 1 to 6 under the corrosion condition of 950 ° C. is 10 of the comparative example. It can be said that it has excellent high-temperature corrosion resistance.
実施例６のシャルピー衝撃試験の衝撃値（Ｊ／ｃｍ２）は、比較例１の衝撃値よりも高く、実施例６は比較例１（特許文献１に記載された合金）に比して靭性が向上していると言える。特に鋳放し材においてはその向上が顕著であり、実施例６の衝撃値は比較例１の約２倍であった。６５０℃、７５０℃、および８５０℃の時効材においても、実施例の衝撃値は２．６Ｊ／ｃｍ２以上を確保し、比較例１を上回る値であった。 The impact value (J / cm 2 ) of the Charpy impact test of Example 6 is higher than the impact value of Comparative Example 1, and Example 6 is tougher than Comparative Example 1 (alloy described in Patent Document 1). Can be said to have improved. In particular, the improvement was remarkable in the as-cast material, and the impact value of Example 6 was about twice that of Comparative Example 1. Even in the aging materials at 650 ° C., 750 ° C., and 850 ° C., the impact value of the example was 2.6 J / cm 2 or more, which was higher than that of Comparative Example 1.
高温腐食試験後の試験片の腐食界面付近の断面のＳＥＭによる観察とＥＰＭＡによる相分析の結果、比較例１ではＣｒが濃化し、Ｎｉが欠乏したσ相が母相中に針状析出し、それが侵食の経路になっていた［図２（Ｂ）の模式図］。一方、実施例１〜６では、母相中に析出する針状のσ相が減少していた［図２（Ａ）の模式図］。すなわち、合金中のＭｏ含有量を減らすことにより、Ｍｏが助長する母相中におけるσ相の時効析出が抑えられ、該σ相の時効析出に伴う靭性低下の問題が改善されるとともに、結果として母相には耐食性の向上に有効な量のＭｏが多く含有されることとなり、靭性及び耐食性の双方を向上させることができると考えられる。 As a result of SEM observation of the cross section near the corrosion interface of the test piece after the high temperature corrosion test and phase analysis by EPMA, Cr was concentrated in Comparative Example 1, and the σ phase lacking Ni was needle-like precipitated in the matrix, That was the path of erosion [schematic diagram of FIG. 2 (B)]. On the other hand, in Examples 1 to 6, the acicular σ phase precipitated in the matrix phase was reduced [schematic diagram in FIG. 2A]. That is, by reducing the Mo content in the alloy, the aging precipitation of the σ phase in the matrix promoted by Mo is suppressed, and the problem of toughness reduction associated with the aging precipitation of the σ phase is improved. The mother phase contains a large amount of Mo effective for improving corrosion resistance, and it is considered that both toughness and corrosion resistance can be improved.
また、Ｍｏが無添加の場合（比較例２）の腐食界面観察結果では、Ｃｒの濃縮したδ相が腐食の起点となっていた。δ相の腐食を抑制するためにはＭｏの添加が有効であり、実施例５のようにＭｏの添加量が０．５ｗｔ％あればその効果が発揮される。 Moreover, in the corrosion interface observation result when Mo is not added (Comparative Example 2), the δ phase enriched with Cr was the starting point of corrosion. In order to suppress the corrosion of the δ phase, addition of Mo is effective, and the effect is exhibited if the addition amount of Mo is 0.5 wt% as in Example 5.
比較例３は、Ｍｏの含有量は３．０ｗｔ％であるが、Ｓｉの含有量が３．０ｗｔ％に設定されている。Ｓｉの含有量が少ないと、Ｃｒ酸化皮膜の内側に形成されるＳｉＯ２保護皮膜が、前記Ｃｒ酸化皮膜を安定させる作用を奏するに足る連続層として形成されないため、９５０℃における耐食性が得られないと考えられる。 In Comparative Example 3, the Mo content is 3.0 wt%, but the Si content is set to 3.0 wt%. If the Si content is small, the SiO 2 protective film formed inside the Cr oxide film is not formed as a continuous layer sufficient to stabilize the Cr oxide film, so that corrosion resistance at 950 ° C. cannot be obtained. it is conceivable that.
このように、高温腐食環境下で耐食性を発揮するとともに靭性の低下しにくい高Ｃｒ−耐高温腐食Ｎｉ基合金を素材とする耐高温腐食部材を用い、焼却処理設備の燃焼炉等の炉内設置物を形成すれば、高温での耐食性に優れ、長期間安定して使用できる炉内設置物を得ることができる。 In this way, high temperature corrosion resistant members made of high Cr-high temperature corrosion resistant Ni-base alloy that exhibits corrosion resistance in a high temperature corrosion environment and does not easily deteriorate toughness are used. If an object is formed, an in-furnace installation that has excellent corrosion resistance at high temperatures and can be used stably for a long period of time can be obtained.
本発明は、都市ごみや産業廃棄物等の廃棄物の焼却処理を行う焼却処理設備における燃焼炉の熱交換器等の、高温腐食環境下で使用される部材を形成する材料として用いられる高Ｃｒ−耐高温腐食Ｎｉ基合金として利用可能である。 The present invention is a high Cr material used as a material for forming a member used in a high temperature corrosive environment, such as a heat exchanger of a combustion furnace in an incineration processing facility that incinerates waste such as municipal waste and industrial waste. -It can be used as a high temperature corrosion resistant Ni-based alloy.
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| JP2012223779A (en) * | 2011-04-18 | 2012-11-15 | Sukegawa Electric Co Ltd | Apparatus for supplying molten metal to die cast sleeve |
| JP2014169472A (en) * | 2013-03-01 | 2014-09-18 | Mitsui Eng & Shipbuild Co Ltd | High temperature corrosion resistant member and heat exchanger |
| CN114397166A (en) * | 2021-12-09 | 2022-04-26 | 阳江合金材料实验室 | Application of potassium permanganate corrosive agent in metallographic corrosion of high-carbon martensitic stainless steel |
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| JP4999042B2 (en) | 2005-01-31 | 2012-08-15 | 三井造船株式会社 | Hot-corrosion resistant metal member, manufacturing method of hot-corrosion resistant metal member |
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| JP2012223779A (en) * | 2011-04-18 | 2012-11-15 | Sukegawa Electric Co Ltd | Apparatus for supplying molten metal to die cast sleeve |
| JP2014169472A (en) * | 2013-03-01 | 2014-09-18 | Mitsui Eng & Shipbuild Co Ltd | High temperature corrosion resistant member and heat exchanger |
| CN114397166A (en) * | 2021-12-09 | 2022-04-26 | 阳江合金材料实验室 | Application of potassium permanganate corrosive agent in metallographic corrosion of high-carbon martensitic stainless steel |
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