JP2019060002A - Protective tube structure of incinerator thermo couple and method for manufacturing the same - Google Patents
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Abstract
【課題】本開示の目的は、基材との密着性がよく、かつクラックなどの発生や剥離を抑制し、設計に準じた機能を発揮できる表面層を持ち、耐酸化性・耐摩耗性が向上した焼却炉用熱電対の保護管用構造体を供給することである。【解決手段】本発明に係る保護管用構造体は、保護管の形状を有する基材と、基材の少なくとも表面側の面に結合している少なくとも２層以上の中間層と、中間層の表面に結合している表面層と、を有し、基材は、クロム又はクロム合金と不可避不純物とからなり、表面層は、基材に含まれる元素Ａ群のうち少なくとも１種と、元素Ｂ群のうち少なくとも２種とを含む合計３種以上の元素を含む合金からなり、合計３種以上の元素のひとつはクロムであり、かつ、表面層は、合金からなる相に前記Ｂ群元素のうち１種の元素の酸化物であるセラミックスが分散している組織を有している。【選択図】図１PROBLEM TO BE SOLVED: To have a surface layer which has good adhesion to a base material, suppresses generation and peeling of cracks, and can exhibit a function according to a design, and has oxidation resistance and wear resistance. It is to supply the structure for the protection tube of the improved thermocouple for the incinerator. SOLUTION: The structure for a protective tube according to the present invention has a base material having the shape of a protective tube, at least two or more intermediate layers bonded to at least a surface side surface of the base material, and a surface of the intermediate layer. The base material is composed of chromium or a chromium alloy and unavoidable impurities, and the surface layer is composed of at least one of the element A group contained in the base material and the element B group. It is composed of an alloy containing a total of 3 or more elements including at least 2 of them, one of the 3 or more elements in total is chromium, and the surface layer is a phase composed of an alloy and among the B group elements. It has a structure in which ceramics, which is an oxide of one element, is dispersed. [Selection diagram] Fig. 1
Description
本開示は、耐熱性及び耐食性に優れた焼却炉用熱電対の保護管用構造体及びその製造方法に関する。 The present disclosure relates to a protective tube structure for an incinerator thermocouple having excellent heat resistance and corrosion resistance, and a method of manufacturing the same.
一般的な耐熱構造体が用いられる高温環境の中には酸化性の雰囲気を伴っている場合がある。また、さらに過酷な環境としては、炉内に対流が生じており、かつその対流に乗ってスケールが舞っているような環境も見られる。これらの環境は、構造体に対して、高温による熱劣化や酸化性雰囲気による劣化を引き起こし、また、対流に乗ったスケールがぶつかることによる摩耗などによって激しい損耗を発生させるので、短寿命化の要因となる。そのため頻繁に該当部材を購入・交換する必要性が生じ、大きなコストを発生させている。従来、基材の耐熱性及び耐食性などを向上させる手段として、基材の表面に耐熱性及び耐食性のあるセラミックスなどの材料をコーティングすることが知られている。セラミックスを含む表面層を形成する方法として、溶射技術やアルミナイズなどのコーティング技術が挙げられる。 Some high temperature environments in which a general heat resistant structure is used may involve an oxidizing atmosphere. Furthermore, as a more severe environment, convection occurs in the furnace, and there is also an environment in which the scale is blown by the convection. These environments cause deterioration of the structure due to high temperature thermal degradation and oxidative atmosphere, and also cause severe wear and tear due to wear caused by the collision of scale on the convection, which causes the shortening of the life span. It becomes. Therefore, it is necessary to frequently purchase and replace the corresponding members, which causes a large cost. Conventionally, as a means for improving the heat resistance and corrosion resistance of a substrate, it is known to coat the surface of the substrate with a material such as ceramics having heat resistance and corrosion resistance. As a method of forming the surface layer containing ceramics, coating techniques, such as a thermal spraying technique and aluminizing, are mentioned.
例えば、基材の表面に、基材の材料とは異なる組成の粉末をセラミックスノズルまたはプラスチックノズルから吹き付ける際に、基材の表面に基材の材料または皮膜の材料と結合力に優れた中間層を形成する異種材料複合部材の製造方法の開示がある（例えば特許文献１を参照。）。 For example, when a powder having a composition different from that of the substrate material is sprayed onto the surface of the substrate from a ceramic nozzle or a plastic nozzle, the intermediate layer has excellent adhesion to the substrate material or coating material on the surface of the substrate. There is a disclosure of a method of manufacturing a dissimilar material composite member that forms a (see, for example, Patent Document 1).
また、耐熱合金の基材表面に、少なくともＡｌ又はＳｉを含む合金層中に酸化物の繊維および粒子が分散された耐酸化皮膜が形成されている耐熱合金の耐酸化被覆構造の開示がある（例えば特許文献２を参照。）。 There is also disclosed an oxidation resistant coating structure of a heat resistant alloy in which an oxide resistant film in which oxide fibers and particles are dispersed in an alloy layer containing at least Al or Si is formed on the surface of a heat resistant alloy substrate (see See, for example, Patent Document 2).
また、Ｃｒ：１０〜３０ｗｔ％、Ｔｉ、Ｎｂ、Ｖ、Ｚｒのうち少なくとも１種類：０．６ｗｔ％以下、Ｃ：０．１ｗｔ％以下、Ｎ：０．０５ｗｔ％以下、Ｓｉ：２．０ｗｔ％以下、Ｍｎ：２．０ｗｔ％以下、残部が鉄および不可避的不純物からなるステンレス鋼の基材と、鉄−クロム−アルミニウムからなるアルミニウム拡散層と０．３〜５．０μｍ厚アルミニウム酸化物皮膜とからなる表面絶縁性に優れたヒーター材料の開示がある（例えば特許文献３を参照。）。 Also, Cr: 10 to 30 wt%, at least one of Ti, Nb, V, and Zr: 0.6 wt% or less, C: 0.1 wt% or less, N: 0.05 wt% or less, Si: 2.0 wt% Hereinafter, Mn: 2.0 wt% or less, the balance being a base material of stainless steel composed of iron and unavoidable impurities, an aluminum diffusion layer composed of iron-chromium-aluminium, and a 0.3 to 5.0 μm thick aluminum oxide film There is a disclosure of a heater material excellent in surface insulation (see, for example, Patent Document 3).
また、母材を金属粉末、耐熱性皮膜形成粉末材等の混合粉末内に埋没させて高温加熱して形成する高温用耐摩耗部材において、母材の皮膜層の硬さをＨｖ７００以上、皮膜厚さを０．０３ｍｍ以上、表面のアルミニウム濃度を１０％以上とする高温用耐摩耗部材の開示がある（例えば特許文献４を参照。）。特許文献４では、皮膜層にはアルミナが形成されているとの開示がある。 In the high temperature wear resistant member formed by immersing the base material in the mixed powder such as metal powder and heat resistant film forming powder material and heating at high temperature, the hardness of the film layer of the base material is Hv 700 or more, and the film thickness There is a disclosure of a high temperature wear resistant member having a length of 0.03 mm or more and a surface aluminum concentration of 10% or more (see, for example, Patent Document 4). Patent Document 4 discloses that alumina is formed on the coating layer.
さらにカロライジング処理を施すことにより、表面に、最表面のＡｌ濃度が１０〜５０重量％のＡｌ拡散浸透層を設けてなる金属製のガス浸炭炉用部品及び冶具の開示がある（例えば特許文献５を参照。）。 Furthermore, there is a disclosure of metal gas carburizing furnace parts and jigs provided with an Al diffusion permeation layer having an Al concentration of 10 to 50% by weight on the surface by subjecting the surface to a calorizing treatment (for example, patent documents See 5).
特許文献１〜５では基材の表面をコーティング膜で被覆する技術が開示されている。しかしながら、いずれのコーティング技術においても基材と表面層との密着性が課題となっている。基材とコーティング層との密着性が充分でなければ、容易にクラックが発生し、基材からコーティング層が剥離し、剥離箇所からの熱劣化、腐蝕、摩耗が発生してしまう。また、基材と表面層との相性が悪いと、表面層の膜厚や組成分布が狙い通りに形成されない場合もあり、表面層は充分な機能を発揮できず、長寿命化を充分に達成できないこととなる。 Patent Documents 1 to 5 disclose techniques for coating the surface of a substrate with a coating film. However, in any of the coating techniques, adhesion between the substrate and the surface layer is a problem. If the adhesion between the substrate and the coating layer is not sufficient, a crack is easily generated, the coating layer is peeled from the substrate, and thermal deterioration, corrosion, and abrasion from the peeled portion occur. In addition, if the compatibility between the substrate and the surface layer is poor, the film thickness and composition distribution of the surface layer may not be formed as intended, and the surface layer can not exhibit a sufficient function to sufficiently achieve long life. It will not be possible.
例えば、溶射によって形成された膜と基材との間には拡散層などの中間層が存在せず、密着性は基材表面の凹凸によるアンカー効果のみの結合力に依存する。このような結合状態の場合、基材と膜との熱膨張率の差によって容易にクラックなどが発生し、剥離に至る。 For example, there is no intermediate layer such as a diffusion layer between the film formed by thermal spraying and the substrate, and the adhesion depends on the bonding force of only the anchor effect due to the unevenness of the substrate surface. In such a bonded state, a crack or the like is easily generated due to the difference in thermal expansion coefficient between the substrate and the film, leading to peeling.
また、鉄やニッケルなどの金属基材に対してアルミナイズ処理を行う手法の場合、膜と基材との間に拡散層が形成され、強固な結合が達成されている。しかし、クロムおよびクロム合金に対して同様の処理を行った場合、生成した膜にはクラックや剥離が多数発生しており、品質の悪いものとなってしまう。 Moreover, in the case of the method of aluminizing the metal base such as iron and nickel, a diffusion layer is formed between the membrane and the base, and a strong bond is achieved. However, when the chromium and the chromium alloy are subjected to the same treatment, a large number of cracks and peelings are generated in the formed film, which results in poor quality.
そのため、保護膜を有する構造体であって、膜の剥離を生じないように密着性を改善しつつ、耐熱性・耐酸化性・耐摩耗性などの特性を、基材が本来持ち合わせている特性よりも向上させることができる構造体は容易には得られていないのが現状である。 Therefore, it is a structure which has a protective film, and the characteristic which a base material originally has characteristics, such as heat resistance, oxidation resistance, abrasion resistance, etc. while improving adhesiveness so that peeling of a film may not occur. Under the present circumstances, a structure that can be improved more than that is not easily obtained.
そこで本開示の目的は、基材との密着性がよく、かつクラックなどの発生や剥離を抑制し、設計に準じた機能を発揮できる表面層を持ち、耐酸化性・耐摩耗性が向上した焼却炉用熱電対の保護管用構造体を供給することである。 Therefore, the object of the present disclosure is to improve the oxidation resistance and wear resistance by having a surface layer which has good adhesion to a substrate, suppresses the occurrence of cracks and the like and peels, and can exhibit a function according to the design. It is to supply a protective tube structure for an incinerator thermocouple.
本発明者らは、上記課題を解決するために鋭意検討したところ、焼却炉用熱電対の保護管用構造体において、基材の表面に２層以上の中間層と表面層としてセラミックスが分散している合金層とを設けることで、上記課題が解決できることを見出し、本発明を完成させた。すなわち本発明に係る焼却炉用熱電対の保護管用構造体は、焼却炉用熱電対の保護管の形状を有する基材と、該基材の少なくとも表面側の面に結合している少なくとも２層以上の中間層と、該中間層の表面に結合している表面層と、を有する焼却炉用熱電対の保護管用構造体であって、前記基材は、クロム又はクロム合金と不可避不純物とからなり、前記表面層は、前記基材に含まれる元素Ａ群のうち少なくとも１種と、元素Ｂ群のうち少なくとも２種とを含む合計３種以上の元素を含む合金からなり、合計３種以上の元素のひとつはクロムであり、かつ、前記表面層は、前記合金からなる相に前記Ｂ群元素のうち１種の元素の酸化物であるセラミックスが分散している組織を有していることを特徴とする。 The inventors of the present invention conducted intensive studies to solve the above problems, and in the structure for the protective tube of the thermocouple for an incinerator, the ceramic was dispersed as two or more intermediate layers and surface layers on the surface of the base material. It has been found that the above problems can be solved by providing an alloy layer and the present invention is completed. That is, the structure for the protective tube of the thermocouple for the incinerator according to the present invention comprises a substrate having the shape of the protective tube for the thermocouple for the incinerator, and at least two layers bonded to at least the surface side of the substrate. A structure for a protective tube of a thermocouple for an incinerator, comprising: the above-mentioned intermediate layer; and a surface layer bonded to the surface of the intermediate layer, wherein the base material is made of chromium or chromium alloy and unavoidable impurities. The surface layer is made of an alloy containing three or more elements in total including at least one of elements A group contained in the base material and at least two of elements B group, and a total of three or more in total One of the elements of is chromium, and the surface layer has a structure in which a ceramic which is an oxide of one of the elements of the group B element is dispersed in a phase consisting of the alloy It is characterized by
本発明に係る焼却炉用熱電対の保護管用構造体では、前記中間層のうち表面層側中間層は少なくとも１層であり、前記表面層側中間層は膜厚方向において組成が均一な層であり、かつ、前記表面層側中間層の各厚みが１〜２００μｍであることが好ましい。基材側中間層と表面層との密着性を向上させることができる。 In the structure for a protective tube of a thermocouple for an incinerator according to the present invention, at least one surface layer side intermediate layer in the intermediate layer is a layer having a uniform composition in the film thickness direction. And each thickness of the surface layer side intermediate layer is preferably 1 to 200 μm. The adhesion between the substrate side intermediate layer and the surface layer can be improved.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記中間層のうち基材側中間層は少なくとも１層であり、前記基材側中間層は前記基材の組成と前記表面層側中間層の組成の間の組成であり、かつ、前記基材側中間層の各厚みが１０〜２００μｍであることが好ましい。前記表面層側中間層と基材との密着性をさらに向上させることができる。 In the structure for a protective tube of a thermocouple for an incinerator according to the present invention, at least one base layer on the base side of the middle layer is the base layer, and the base layer on the base side is the composition of the base and the surface layer side. It is preferable that it is a composition between the compositions of an intermediate | middle layer, and each thickness of the said base material side intermediate | middle layer is 10-200 micrometers. The adhesion between the surface layer side intermediate layer and the substrate can be further improved.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記中間層のうち基材側中間層は少なくとも１層であり、前記基材側中間層は前記基材の組成と前記表面層側中間層の組成とを連続的につなぐ傾斜機能層であり、かつ、前記基材側中間層の各厚みは１０〜２００μｍであることが好ましい。前記表面層側中間層と基材との密着性をさらに向上させることができる。 In the structure for a protective tube of a thermocouple for an incinerator according to the present invention, at least one base layer on the base side of the middle layer is the base layer, and the base layer on the base side is the composition of the base and the surface layer side. It is a gradient functional layer which continuously connects the composition of the intermediate layer, and each thickness of the substrate side intermediate layer is preferably 10 to 200 μm. The adhesion between the surface layer side intermediate layer and the substrate can be further improved.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記中間層の総厚みが１１〜４００μｍであることが好ましい。表面層と基材との密着性が高まり、剥離、クラックの発生が少ない。 It is preferable that the total thickness of the said intermediate | middle layer is 11-400 micrometers in the structure for protective tubes of the thermocouple for incinerators which concerns on this invention. The adhesion between the surface layer and the base material is enhanced, and the occurrence of peeling and cracking is reduced.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記表面層に分散しているセラミックスは、表面に垂直な断面において、粒径１〜５０μｍの範囲にあるセラミックス粒子が面積比で４０％以上を占めていることが好ましい。構造体の耐酸化性・耐摩耗性が向上し、長寿命化を充分に達成できる。 In the protective tube structure of the thermocouple for an incinerator according to the present invention, the ceramic dispersed in the surface layer has, in a cross section perpendicular to the surface, ceramic particles having a particle diameter in the range of 1 to 50 μm in area ratio 40 It is preferable to occupy at least%. The oxidation resistance and wear resistance of the structure are improved, and the long life can be sufficiently achieved.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記表面層の厚みが１０〜２００μｍであることが好ましい。構造体の耐酸化性・耐摩耗性が向上し、表面層での剥離、クラックの発生が少ない。 It is preferable that the thickness of the said surface layer is 10-200 micrometers in the structure for protective tubes of the thermocouple for incinerators which concerns on this invention. Oxidation resistance and wear resistance of the structure are improved, and the occurrence of peeling and cracking in the surface layer is reduced.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記表面層側から測定した前記構造体の硬さがビッカース硬度で４００Ｈｖ以上であることが好ましい。構造体の摩耗を抑制することができる。 In the protective tube structural body of the thermocouple for an incinerator according to the present invention, the hardness of the structural body measured from the surface layer side is preferably 400 Hv or more in Vickers hardness. It is possible to suppress the wear of the structure.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記中間層は、Ｆｅ、Ｎｉ、Ｐｄの少なくとも１種を含み、Ｆｅ、Ｎｉ、Ｐｄの少なくとも１種は元素Ｂ群に属することが好ましい。表面層と基材とを強固に結合し、剥離、クラックの発生が抑えられている。 In the protective tube structure for a thermocouple for an incinerator according to the present invention, the intermediate layer contains at least one of Fe, Ni, and Pd, and at least one of Fe, Ni, and Pd belongs to the element group B. preferable. The surface layer and the base material are strongly bonded, and the occurrence of peeling and cracking is suppressed.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記表面層に分散している前記セラミックスはＢｅ、Ｍｇ、Ａｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｃｒ、Ｚｒ、Ｈｆ、Ｌａ、Ｃｅ、Ｙ、Ｓｃのうち少なくとも１つの元素の酸化物と不可避不純物とからなることが好ましい。構造体の耐酸化性・耐摩耗性がさらに向上する。 In the protective tube structure for a thermocouple for an incinerator according to the present invention, the ceramic dispersed in the surface layer is Be, Mg, Al, Si, Ca, Ti, Cr, Zr, Hf, La, Ce, Y And Sc and is preferably composed of an oxide of at least one element and unavoidable impurities. The oxidation resistance and wear resistance of the structure are further improved.
本発明に係る焼却炉用熱電対の保護管用構造体の製造方法は、本発明に係る焼却炉用熱電対の保護管用構造体の製造方法であって、クロム又はクロム合金と不可避不純物とからなる基材の表面に、堆積、拡散又は含浸によって元素Ｂ群のうちの少なくとも１種を含む前処理層を形成する第１工程と、前記前処理層の表面を、元素Ｂ群のうちの他の少なくとも１種である元素で被覆することによって被覆層を形成する第２工程と、前記基材と前記前処理層と前記被覆層とを合金化させることによって、前記中間層及び前記表面層を形成する第３工程と、を有し、前記表面層の合金は、前記基材由来の元素Ａ群のうち少なくとも１種と、前記前処理層に由来する元素Ｂ群のうちの少なくとも１種と、前記被覆層に由来する元素Ｂ群のうちの他の少なくとも１種とを含む合計３種以上の元素を含む合金であり、かつ、合計３種以上の元素のひとつはクロムであり、前記表面層にはセラミックスが分散しており、前記セラミックスは、前記被覆層に由来する元素の酸化物であることを特徴とする。 The method for producing a protective tube structure of a thermocouple for an incinerator according to the present invention is a method for producing a protective tube structure for a thermocouple for an incinerator according to the present invention, which comprises chromium or a chromium alloy and unavoidable impurities. A first step of forming a pretreatment layer containing at least one of element B group by deposition, diffusion or impregnation on the surface of a substrate, and a surface of the pretreatment layer, the other of element B group The second step of forming a covering layer by covering with at least one element, and forming the intermediate layer and the surface layer by alloying the substrate, the pretreatment layer, and the covering layer And the alloy of the surface layer is at least one of the element A group derived from the base material, and at least one of the element B group derived from the pretreatment layer. Another small amount of the element B group derived from the covering layer The alloy is an alloy containing a total of three or more elements including at least one, and one of a total of three or more elements is chromium, and the ceramic is dispersed in the surface layer, and the ceramic is It is characterized in that it is an oxide of an element derived from the covering layer.
本発明に係る焼却炉用熱電対の保護管用構造体の製造方法は、前記堆積、拡散又は含浸は、メッキ、溶射、拡散接合又は熱拡散の少なくともいずれか一つによって行われることが好ましい。基材に対して密着性のよい前処理層を形成することができる。 In the method of manufacturing a protective tube structure for a thermocouple for an incinerator according to the present invention, the deposition, diffusion or impregnation is preferably performed by at least one of plating, thermal spraying, diffusion bonding or thermal diffusion. It is possible to form a pretreatment layer having good adhesion to the substrate.
本発明に係る焼却炉用熱電対の保護管用構造体の製造方法では、前記前処理層を形成する第１工程において、前記基材に１〜１００μｍの少なくとも１層の層を堆積、拡散または含浸させることが好ましい。好適な膜厚の中間層と表面層を形成することができる。 In the method for manufacturing a protective tube structure of a thermocouple for an incinerator according to the present invention, in the first step of forming the pretreatment layer, at least one layer of 1 to 100 μm is deposited, diffused or impregnated on the substrate. It is preferable to It is possible to form an intermediate layer and a surface layer of suitable thickness.
本発明に係る焼却炉用熱電対の保護管用構造体の製造方法では、前記前処理層を形成する第１工程において、堆積、拡散または含浸される材質がＦｅ、Ｎｉ、Ｐｄ、Ｆｅ合金、Ｎｉ合金又はＰｄ合金、及び不可避不純物を含むことが好ましい。表面層と基材とを強固に結合する中間層を形成することができる。 In the method for manufacturing a protective tube structure of a thermocouple for an incinerator according to the present invention, in the first step of forming the pretreatment layer, the material deposited, diffused or impregnated is Fe, Ni, Pd, Fe alloy, Ni Preferably, it contains an alloy or Pd alloy, and unavoidable impurities. It is possible to form an intermediate layer which firmly bonds the surface layer and the substrate.
本開示によれば、基材との密着性がよく、かつクラックなどの発生や剥離を抑制し、設計に準じた機能を発揮できる表面層を持ち、耐酸化性・耐摩耗性が向上した焼却炉用熱電対の保護管用構造体を供給することができる。 According to the present disclosure, the incineration has a good adhesion with the base material, suppresses the occurrence of cracks and the like and peels, has a surface layer capable of exhibiting a function according to the design, and has improved oxidation resistance and wear resistance. A furnace tube protective tube structure can be supplied.
以降、本発明について実施形態を示して詳細に説明するが本発明はこれらの記載に限定して解釈されない。本発明の効果を奏する限り、実施形態は種々の変形をしてもよい。 Hereinafter, the present invention will be described in detail by way of embodiments, but the present invention is not interpreted as being limited to these descriptions. The embodiment may be variously modified as long as the effects of the present invention are exhibited.
（焼却炉用熱電対の保護管用構造体）
まず、本実施形態に係る焼却炉用熱電対の保護管用構造体の製造方法について説明する。図１に示すように、本実施形態に係る焼却炉用熱電対の保護管用構造体１は、焼却炉用熱電対の保護管の形状を有する基材２と、基材２の少なくとも表面側の面に結合している少なくとも２層以上の中間層３と、中間層３の表面に結合している表面層４と、を有する。
(Structure for protective tube of thermocouple for incinerator)
First, a method of manufacturing a protective tube structure for a thermocouple for an incinerator according to the present embodiment will be described. As shown in FIG. 1, the protective tube structural body 1 of the thermocouple for an incinerator according to the present embodiment includes a substrate 2 having the shape of the protective tube of the thermocouple for an incinerator, and at least the surface side of the substrate 2 It has at least two or more intermediate layers 3 bonded to the surface, and a surface layer 4 bonded to the surface of the intermediate layer 3.
図１では、保護管用構造体１の中間層３が基材側中間層３ａと表面層側中間層３ｂの２つの中間層を有している形態を示したが、中間層３が３つ以上の中間層を有している形態であってもよい。また、図１では、保護管形状の基材２の表面側に中間層３及び表面層４有する形態を示したが、保護管の表面側及び管の内面側の両方に中間層３及び表面層４を有する形態であってもよい。さらに保護管の開口部の端面に中間層３及び表面層４を設けてもよい。 In FIG. 1, the intermediate layer 3 of the protective tube structure 1 has a form in which the two intermediate layers of the base material side intermediate layer 3 a and the surface layer side intermediate layer 3 b are provided. It may be in a form having an intermediate layer of Moreover, although the form which has the intermediate layer 3 and the surface layer 4 on the surface side of the base material 2 of a protective tube shape was shown in FIG. 1, the intermediate layer 3 and the surface layer are shown on the surface side of a protective tube and the inner surface side of a pipe. It may be a form having four. Furthermore, the intermediate layer 3 and the surface layer 4 may be provided on the end face of the opening of the protective tube.
本実施形態に係る焼却炉用熱電対の保護管用構造体１では、基材２は、クロム又はクロム合金と不可避不純物とからなり、表面層４は、基材２に含まれる元素Ａ群のうち少なくとも１種と、元素Ｂ群のうち少なくとも２種とを含む合計３種以上の元素を含む合金からなり、合計３種以上の元素のひとつはクロムであり、かつ、表面層４は、前記合金からなる相にＢ群元素のうち１種の元素の酸化物であるセラミックスが分散している組織を有している。 In the protective tube structural body 1 of the thermocouple for the incinerator according to the present embodiment, the base material 2 is made of chromium or chromium alloy and unavoidable impurities, and the surface layer 4 is an element A group contained in the base material 2. It consists of an alloy containing a total of three or more elements in total including at least one type and at least two types in the element B group, one of a total of three or more types of elements is chromium, and the surface layer 4 is the alloy In the phase consisting of the above, there is a structure in which a ceramic which is an oxide of one of the B group elements is dispersed.
基材２は、クロム又はクロム合金と不可避不純物とからなる。クロム合金に含まれる金属としては、Ｃｒを必須とし、Ｆｅ、Ｗ、Ｎｂ、Ｔｉなどの金属である。クロム合金は、含有される元素の中ではＣｒが原子百分率(ａｔ％)で最も多く含まれていることを特徴とする。クロム合金は耐熱性合金として、例えば焼却炉内部の温度を測る熱電対の保護管に用いられるが、充分な耐酸化性・耐摩耗性がなく、寿命が短い。この問題を解決するために本発明が有効である。例えば焼却炉などの高温かつ酸化性雰囲気、さらにスケールを含む対流が発生しているような環境下で使用される熱電対の保護管として適性がある。 The substrate 2 is made of chromium or chromium alloy and unavoidable impurities. As a metal contained in a chromium alloy, Cr is essential, and metals such as Fe, W, Nb, and Ti are used. The chromium alloy is characterized in that Cr is contained most in atomic percent (at%) among the contained elements. Chromium alloy is used as a heat-resistant alloy, for example, for a protective tube of a thermocouple that measures the temperature inside the incinerator, but there is no sufficient oxidation resistance and wear resistance, and the life is short. The present invention is effective to solve this problem. For example, it is suitable as a protective tube of a thermocouple used in a high temperature and oxidizing atmosphere such as an incinerator and an environment where convection including scale is generated.
元素Ａ群は基材２に含まれる元素であり、Ｃｒ、Ｆｅ、Ｗ、Ｎｂ及びＴｉから選ばれる少なくとも１種の元素である。元素Ｂ群は、例えば、基材２又は製造過程における前処理層及び／または被覆層に由来する元素であり、Ｆｅ、Ｎｉ、Ｐｄ、Ｂｅ、Ｍｇ、Ａｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｃｒ、Ｚｒ、Ｈｆ、Ｌａ、Ｃｅ、Ｙ及びＳｃから選ばれる少なくとも２種である。Ｃｒ、Ｆｅ及びＴｉは、元素Ａ群と元素Ｂ群の両方に属しているが、これらの元素が選択される場合には、基材２に由来してもよく、或いは前処理層に由来してもよく、被覆層に由来してもよく、基材２及び前処理層に由来してもよく、基材２及び被覆層に由来してもよく、前処理層及び被覆層に由来してもよく、基材及び前処理層及び被覆層に由来してもよい。表面層４は、元素Ａ群のうち少なくとも１種と、元素Ｂ群のうち少なくとも２種とを含む合計３種以上の元素を含む合金（以降、合金Ｘともいう。）からなるが、合計３種以上の元素のひとつは必ずＣｒである。 The element A group is an element contained in the base material 2 and is at least one element selected from Cr, Fe, W, Nb and Ti. The element B group is, for example, an element derived from the pretreatment layer and / or the covering layer in the base material 2 or the production process, and Fe, Ni, Pd, Be, Mg, Al, Si, Ca, Ti, Cr, Zr , Hf, La, Ce, Y and Sc. Cr, Fe and Ti belong to both of the element A group and the element B group, but when these elements are selected, they may be derived from the base material 2 or derived from the pretreatment layer May be derived from the coating layer, may be derived from the substrate 2 and the pretreatment layer, may be derived from the substrate 2 and the coating layer, and may be derived from the pretreatment layer and the coating layer It may also be derived from the substrate and the pretreatment layer and the covering layer. The surface layer 4 is made of an alloy containing three or more elements in total including at least one element in the element group A and at least two elements in the element group B (hereinafter also referred to as alloy X), but a total of three. One of the elements above the species is always Cr.
表面層４は、合金Ｘからなる相にＢ群元素のうち１種の元素の酸化物であるセラミックスが分散している組織を有している。構造体の耐酸化性・耐摩耗性がさらに向上する。元素Ｂ群のうちセラミックス化する元素は、例えば、Ｂｅ、Ｍｇ、Ａｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｃｒ、Ｚｒ、Ｈｆ、Ｌａ、Ｃｅ、Ｙ、Ｓｃである。ある元素がセラミックス化しても、合金Ｘからなる相には、合計３種以上の元素が含まれている。すなわち、セラミックス化した元素は、セラミックスとマトリックスである合金相の両方に存在している。なお、セラミックスには、不可避不純物の酸化物も含まれる場合がある。 The surface layer 4 has a structure in which a ceramic which is an oxide of one of the B group elements is dispersed in a phase made of an alloy X. The oxidation resistance and wear resistance of the structure are further improved. Among the element B group, the element to be ceramicized is, for example, Be, Mg, Al, Si, Ca, Ti, Cr, Zr, Hf, La, Ce, Y, Sc. Even if a certain element is made ceramic, the phase consisting of alloy X contains a total of three or more elements. That is, the element made ceramic is present in both the ceramic and the alloy phase which is the matrix. The ceramics may also contain oxides of unavoidable impurities.
合金相Ｘとセラミックスの好ましい組み合わせとしては、例えば、合金相（Ｃｒ、Ａｌ、Ｆｅ）及びセラミックス（Ａｌ２Ｏ３）の組み合わせである。 A preferable combination of the alloy phase X and the ceramic is, for example, a combination of an alloy phase (Cr, Al, Fe) and a ceramic (Al 2 O 3 ).
表面層４に分散しているセラミックスは、表面に垂直な断面において、粒径１〜５０μｍの範囲にあるセラミックス粒子が面積比で４０％以上を占めていることが好ましい。電子顕微鏡における観察において、視野に含まれる粒子の８０％以上（ただし、個数の比率）が粒径１〜５０μｍの範囲にあることが好ましい。粒径の範囲は、より好ましくは１〜４０μｍの範囲、さらに好ましくは１〜２０μｍの範囲である。粒径が１μｍ未満のセラミックス粒子が多くなると耐酸化性・耐摩耗性の向上に充分に寄与できない場合がある。一方、粒径が５０μｍを超えるセラミックス粒子が多くなると径の大きすぎるセラミックスは脱離やクラックの要因となる。セラミックス粒子の面積比は４０％以上が好ましく、より好ましくは５０％以上、さらに好ましくは６０％以上である。構造体の耐酸化性・耐摩耗性が向上し、長寿命化を充分に達成できる。セラミックスが占める面積が４０％未満の場合は耐酸化性・耐摩耗性の向上に充分に寄与できない。 In the ceramic dispersed in the surface layer 4, ceramic particles having a particle diameter in the range of 1 to 50 μm preferably occupy 40% or more in area ratio in a cross section perpendicular to the surface. In observation with an electron microscope, it is preferable that 80% or more (however, the ratio of the number) of particles contained in the visual field be in the range of 1 to 50 μm in particle diameter. The range of the particle size is more preferably in the range of 1 to 40 μm, and still more preferably in the range of 1 to 20 μm. When the number of ceramic particles having a particle size of less than 1 μm increases, it may not be able to sufficiently contribute to the improvement of oxidation resistance and wear resistance. On the other hand, if the number of ceramic particles having a particle size of more than 50 μm increases, ceramics having too large a diameter cause detachment or cracking. The area ratio of the ceramic particles is preferably 40% or more, more preferably 50% or more, and still more preferably 60% or more. The oxidation resistance and wear resistance of the structure are improved, and the long life can be sufficiently achieved. If the area occupied by the ceramic is less than 40%, it can not sufficiently contribute to the improvement of oxidation resistance and wear resistance.
表面層４の厚みが１０〜２００μｍであることが好ましく、より好ましくは１０〜１５０μｍ、さらに好ましくは１０〜１００μｍである。構造体の耐酸化性・耐摩耗性が向上し、表面層での剥離、クラックの発生が少ない。表面層４の厚みが１０μｍ未満であると耐酸化性・耐摩耗性の向上に充分に寄与できず、２００μｍを超えると表面層４の脱離やクラックの要因となる。 The thickness of the surface layer 4 is preferably 10 to 200 μm, more preferably 10 to 150 μm, and still more preferably 10 to 100 μm. Oxidation resistance and wear resistance of the structure are improved, and the occurrence of peeling and cracking in the surface layer is reduced. If the thickness of the surface layer 4 is less than 10 μm, it can not sufficiently contribute to the improvement of the oxidation resistance and the wear resistance, and if it exceeds 200 μm, it causes the detachment and cracking of the surface layer 4.
本実施形態に係る焼却炉用熱電対の保護管用構造体１では、中間層３のうち表面層側中間層３ｂは少なくとも１層であり、表面層側中間層３ｂは膜厚方向において組成が均一な層であり、かつ、表面層側中間層３ｂの各厚みが１〜１００μｍであることが好ましい。表面層と基材側中間層３ａとの密着性を向上させることができる。図１では、表面層側中間層３ｂが１層である形態を図示したが、２層以上であってもよい。表面層側中間層３ｂが１層である場合、膜厚方向において組成が均一な層であり、その厚みは１〜２００μｍであることが好ましく、より好ましくは１〜１５０μｍ、さらに好ましくは１〜１００μｍである。表面層側中間層３ｂが２層以上である場合、各層においてそれぞれ膜厚方向において組成が均一な層であり、その厚みは１〜２００μｍであることが好ましく、より好ましくは１〜１５０μｍ、さらに好ましくは１〜１００μｍである。表面層側中間層３ｂが２層以上である場合、各層は互いに異なる組成を有するが、それぞれ膜厚方向において組成が均一な層となっている。組成が均一な層の「均一」とは、ＳＥＭ−ＥＤＸでの観察において、層内でブレが±１０％を超える組成の偏在が存在しないことをいう。 In the protective tube structural body 1 of the thermocouple for the incinerator according to the present embodiment, at least one surface layer side intermediate layer 3b of the intermediate layer 3 is used, and the surface layer side intermediate layer 3b has a uniform composition in the film thickness direction. It is preferable that each thickness of the surface layer side intermediate layer 3b is 1 to 100 μm. The adhesion between the surface layer and the base material side intermediate layer 3a can be improved. Although the surface layer side intermediate | middle layer 3b illustrated the form which is 1 layer in FIG. 1, two or more layers may be sufficient. When the surface layer side intermediate layer 3b is a single layer, it is a layer having a uniform composition in the film thickness direction, and its thickness is preferably 1 to 200 μm, more preferably 1 to 150 μm, still more preferably 1 to 100 μm. It is. When the surface layer side intermediate layer 3b is two or more layers, each layer is a layer having a uniform composition in the film thickness direction, and its thickness is preferably 1 to 200 μm, more preferably 1 to 150 μm, further preferably Is 1 to 100 μm. When the surface layer side intermediate layer 3b is two or more layers, each layer has a composition different from each other, but each layer is a layer having a uniform composition in the film thickness direction. The "uniform" of a layer having a uniform composition means that, in observation with SEM-EDX, there is no uneven distribution of composition with a deviation of more than ± 10% in the layer.
中間層３は、Ｆｅ、Ｎｉ、Ｐｄの少なくとも１種を含み、Ｆｅ、Ｎｉ、Ｐｄの少なくとも１種は元素Ｂ群に属することが好ましい。表面層と基材とを強固に結合し、剥離、クラックの発生が抑えられている。 The intermediate layer 3 preferably contains at least one of Fe, Ni, and Pd, and at least one of Fe, Ni, and Pd preferably belongs to the element B group. The surface layer and the base material are strongly bonded, and the occurrence of peeling and cracking is suppressed.
本実施形態に係る焼却炉用熱電対の保護管用構造体１では、中間層３のうち基材側中間層３ａは少なくとも１層であり、基材側中間層３ａは基材２の組成と表面層側中間層３ｂの組成の間の組成を有している。また、より好ましくは基材側中間層３ａは基材２の組成と表面層側中間層３ｂの組成とを連続的につなぐ傾斜機能層である。基材側中間層３ａの各厚みは１０〜２００μｍであることが好ましい。表面層と基材との密着性をさらに向上させることができる。図１では、基材側中間層３ａが１層である形態を図示したが、２層以上であってもよい。基材側中間層３ａが１層である場合、その基材側中間層３ａが基材２の組成と表面層側中間層３ｂの組成の間の組成を有するか、基材２の組成と表面層側中間層３ｂの組成とを連続的につなぐ傾斜機能層となる。基材側中間層３ａが２層以上である場合、その２層以上が全体として、基材２の組成と表面層側中間層３ｂの組成の間の組成を有するか、基材２の組成と表面層側中間層３ｂの組成とを連続的につなぐ傾斜機能層となっており、かつ、２層以上の各層との間に、何らかの境界が見出される。基材側中間層３ａの各厚みは、より好ましくは１０〜１５０μｍ、さらに好ましくは１０〜１００μｍである。 In the structure 1 for a protective tube of a thermocouple for an incinerator according to the present embodiment, the intermediate layer 3 includes at least one base layer 3a of the base layer, and the base layer 3a has a composition and a surface of the base 2 It has a composition between the compositions of the layer side middle layer 3b. Further, more preferably, the base material side intermediate layer 3a is a gradient functional layer which continuously connects the composition of the base material 2 and the composition of the surface layer side intermediate layer 3b. It is preferable that each thickness of the base material side intermediate | middle layer 3a is 10-200 micrometers. The adhesion between the surface layer and the substrate can be further improved. Although FIG. 1 illustrates a mode in which the base material side intermediate layer 3a is a single layer, it may have two or more layers. When the substrate side intermediate layer 3a is a single layer, whether the substrate side intermediate layer 3a has a composition between the composition of the substrate 2 and the composition of the surface layer side intermediate layer 3b, or the composition and surface of the substrate 2 It becomes a gradient functional layer which connects the composition of layer side middle class 3b continuously. When the substrate side intermediate layer 3a is two or more layers, the two or more layers may have a composition between the composition of the substrate 2 and the composition of the surface layer side intermediate layer 3b as a whole or It is a functionally gradient layer that continuously connects the composition of the surface layer side intermediate layer 3b, and some boundary is found between two or more layers. The thickness of each of the substrate-side intermediate layers 3a is more preferably 10 to 150 μm, still more preferably 10 to 100 μm.
中間層３の総厚みが１１〜４００μｍであることが好ましい。より好ましくは１１〜３００μｍ、さらに好ましくは１１〜２００μｍである。表面層と基材との密着性が高まり、中間層での剥離、クラックの発生が少ない。中間層３の総厚みが１１μｍ未満であると、中間層としての充分な機能を発揮できず、クラックなどの発生を充分に抑制できない。中間層３の総厚みが４００μｍを超えると保護管用構造体の製品径（以降、径ともいう。）の増加が大きくなりすぎるため、構造体としての取り扱いに支障をきたす。 The total thickness of the intermediate layer 3 is preferably 11 to 400 μm. More preferably, it is 11-300 micrometers, More preferably, it is 11-200 micrometers. The adhesion between the surface layer and the base material is enhanced, and the occurrence of peeling and cracking in the intermediate layer is reduced. If the total thickness of the intermediate layer 3 is less than 11 μm, a sufficient function as the intermediate layer can not be exhibited, and the occurrence of cracks and the like can not be sufficiently suppressed. If the total thickness of the intermediate layer 3 exceeds 400 μm, the increase in the product diameter (hereinafter also referred to as the diameter) of the protective pipe structure becomes too large, which causes a problem in handling as a structural body.
本実施形態に係る焼却炉用熱電対の保護管用構造体１では、表面層４側から測定した構造体１の硬さがビッカース硬度で４００Ｈｖ以上であることが好ましい。より好ましくは５００Ｈｖ以上である。構造体の摩耗を抑制することができる。測定条件は、表面層４を形成した構造体１の表面から２．５ｋｇの荷重でビッカース硬度をＪＩＳ Ｚ ２２４４に従って測定する。ビッカース硬度が４００Ｈｖ未満の場合、耐摩耗性の向上に充分に寄与することができない場合がある。 In the protective tube structural body 1 of the thermocouple for an incinerator according to the present embodiment, the hardness of the structural body 1 measured from the surface layer 4 side is preferably 400 Hv or more in Vickers hardness. More preferably, it is 500 Hv or more. It is possible to suppress the wear of the structure. Measurement conditions measure Vickers hardness according to JIS Z 2244 under a load of 2.5 kg from the surface of the structure 1 on which the surface layer 4 is formed. If the Vickers hardness is less than 400 Hv, it may not be able to sufficiently contribute to the improvement of the wear resistance.
本発明に係る焼却炉用熱電対の保護管用構造体では、前記中間層は、Ｆｅ、Ｎｉ、Ｐｄの少なくとも１種を含み、Ｆｅ、Ｎｉ、Ｐｄの少なくとも１種は元素Ｂ群に属することが好ましい。表面層と基材とを強固に結合し、剥離、クラックの発生が抑えられている。 In the protective tube structure for a thermocouple for an incinerator according to the present invention, the intermediate layer contains at least one of Fe, Ni, and Pd, and at least one of Fe, Ni, and Pd belongs to the element group B. preferable. The surface layer and the base material are strongly bonded, and the occurrence of peeling and cracking is suppressed.
基材２、中間層３及び表面層４の具体的な組成の組み合わせについて例示する。基材２の材質はクロム又はクロム合金である。基材側中間層３ａは基材２と中間層３ｂの間の組成もしくは傾斜組成を有し、基材側中間層３ａ内において基材２から表面層側中間層３ｂへ向かって、Ｃｒ「多」からＣｒ「少」に組成が変化する。また、基材側中間層３ａ内において基材２から表面層側中間層３ｂへ向かって、Ａｌ「少」からＡｌ「多」に組成が変化する。また、基材側中間層３ａ内において基材２から表面層側中間層３ｂへ向かって、Ｆｅ「少」からＦｅ「多」に組成が変化する。表面層側中間層３ｂは均一組成層であり、ＦｅとＣｒとＡｌを含有する。なお、Ｆｅの存在比率（ａｔ％）は表面層側中間層３ｂの方が基材側中間層３ａよりも高い。Ｃｒの存在比率（ａｔ％）は表面層側中間層３ｂの方が基材側中間層３ａよりも低い。Ａｌの存在比率（ａｔ％）は表面層側中間層３ｂの方が基材側中間層３ａよりも高い。ただし、Ａｌの存在比率（ａｔ％）は表面層４の方が表面層側中間層３ｂよりも高い。表面層４の合金Ｘは、Ａｌ‐Ｆｅ‐Ｃｒ合金であり、セラミックスはアルミナ粒子である。アルミナ粒子は、表面層４のみに存在する。 It illustrates about the combination of the specific composition of the base material 2, the intermediate | middle layer 3, and the surface layer 4. FIG. The material of the substrate 2 is chromium or a chromium alloy. The substrate side intermediate layer 3a has a composition or a gradient composition between the substrate 2 and the intermediate layer 3b, and in the substrate side intermediate layer 3a, the Cr The composition changes from Cr to Cr "small". Further, in the base material side intermediate layer 3a, the composition changes from Al “small” to Al “many” from the base material 2 to the surface layer side intermediate layer 3b. Moreover, in the base material side intermediate layer 3a, the composition changes from Fe "small" to Fe "many" from the base material 2 to the surface layer side intermediate layer 3b. The surface layer side intermediate layer 3b is a uniform composition layer and contains Fe, Cr and Al. In addition, the abundance ratio (at%) of Fe is higher in the surface layer side intermediate layer 3b than in the base material side intermediate layer 3a. The abundance ratio (at%) of Cr is lower in the surface layer side intermediate layer 3 b than in the substrate side intermediate layer 3 a. The abundance ratio (at%) of Al is higher in the surface layer side intermediate layer 3 b than in the substrate side intermediate layer 3 a. However, the abundance ratio (at%) of Al is higher in the surface layer 4 than in the surface layer side intermediate layer 3 b. The alloy X of the surface layer 4 is an Al-Fe-Cr alloy, and the ceramic is alumina particles. Alumina particles are present only in the surface layer 4.
（焼却炉用熱電対の保護管用構造体の製造方法）
次に、本実施形態に係る焼却炉用熱電対の保護管用構造体の製造方法について説明する。本実施形態に係る焼却炉用熱電対の保護管用構造体の製造方法は、クロム又はクロム合金と不可避不純物とからなる基材の表面に、堆積、拡散又は含浸によって元素Ｂ群のうちの少なくとも１種を含む前処理層を形成する第１工程と、前記前処理層の表面を、元素Ｂ群のうちの他の少なくとも１種である元素で被覆することによって被覆層を形成する第２工程と、前記基材と前記前処理層と前記被覆層とを合金化させることによって、前記中間層及び前記表面層を形成する第３工程と、を有する。第３工程において、前記表面層の合金は、前記基材由来の元素Ａ群のうち少なくとも１種と、前記前処理層に由来する元素Ｂ群のうちの少なくとも１種と、前記被覆層に由来する元素Ｂ群のうちの他の少なくとも１種とを含む合計３種以上の元素を含む合金であり、かつ、合計３種以上の元素のひとつはクロムであり、前記表面層にはセラミックスが分散しており、前記セラミックスは、前記被覆層に由来する元素の酸化物である。
(Method of manufacturing protective tube structure for thermocouple for incinerator)
Next, the manufacturing method of the protective tube structure of the thermocouple for the incinerator according to the present embodiment will be described. The method for producing a protective tube structure of a thermocouple for an incinerator according to the present embodiment includes at least one of elements B group by deposition, diffusion or impregnation on the surface of a substrate comprising chromium or chromium alloy and unavoidable impurities. A first step of forming a pretreatment layer containing a species, and a second step of coating the surface of the pretreatment layer with at least one other element of the group of elements B to form a coating layer And a third step of forming the intermediate layer and the surface layer by alloying the base material, the pretreatment layer, and the covering layer. In the third step, the alloy of the surface layer is derived from at least one of the element group A derived from the base material, at least one of the element group B derived from the pretreatment layer, and the covering layer Containing at least one other element of the group B elements, and containing three or more elements in total, and one of the three or more elements in total is chromium, and the ceramic is dispersed in the surface layer. The ceramic is an oxide of an element derived from the covering layer.
（第１工程）
第１工程では、クロム又はクロム合金と不可避不純物とからなる基材の表面に前処理層を形成する。前処理層は、基材の表面に、堆積、拡散又は含浸によって形成する。ここで、堆積、拡散又は含浸は、メッキ、溶射、拡散接合又は熱拡散の少なくともいずれか一つによって行われることが好ましい。基材に対して密着性のよい前処理層を形成することができる。具体的には、堆積によって形成した前処理層には、例えばメッキ法又は溶射法によって基材２の表面に形成した被膜が含まれる。拡散によって形成した前処理層には、例えば拡散接合又は熱拡散によって基材２の表面に形成された接合層が含まれる。前処理層は元素Ｂ群のうちの少なくとも１種を含む。元素Ｂ群は、例えばＦｅ、Ｎｉ、Ｐｄ、Ｂｅ、Ｍｇ、Ａｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｃｒ、Ｚｒ、Ｈｆ、Ｌａ、Ｃｅ、Ｙ、Ｓｃのうちの少なくとも１種である。前処理層は元素Ｂ群のうちの少なくとも１種をメッキ液、溶射粉末、箔、粉末又は融液に含ませて形成する。
(Step 1)
In the first step, a pretreatment layer is formed on the surface of the substrate comprising chromium or chromium alloy and unavoidable impurities. The pretreatment layer is formed on the surface of the substrate by deposition, diffusion or impregnation. Here, the deposition, diffusion or impregnation is preferably performed by at least one of plating, thermal spraying, diffusion bonding or thermal diffusion. It is possible to form a pretreatment layer having good adhesion to the substrate. Specifically, the pretreatment layer formed by deposition includes a coating formed on the surface of the substrate 2 by, for example, a plating method or a thermal spraying method. The pretreatment layer formed by diffusion includes, for example, a bonding layer formed on the surface of the substrate 2 by diffusion bonding or heat diffusion. The pretreatment layer contains at least one of element B group. The element B group is, for example, at least one of Fe, Ni, Pd, Be, Mg, Al, Si, Ca, Ti, Cr, Zr, Hf, La, Ce, Y, and Sc. The pretreatment layer is formed by including at least one of element B in a plating solution, a thermal spray powder, a foil, a powder or a melt.
前処理層を形成するために、堆積、拡散または含浸される材質がＦｅ、Ｎｉ、Ｐｄ、Ｆｅ合金、Ｎｉ合金又はＰｄ合金、及び不可避不純物を含むことが好ましい。表面層と基材とを強固に結合する中間層を形成することができる。 In order to form the pretreatment layer, the material to be deposited, diffused or impregnated preferably contains Fe, Ni, Pd, a Fe alloy, a Ni alloy or a Pd alloy, and unavoidable impurities. It is possible to form an intermediate layer which firmly bonds the surface layer and the substrate.
基材２に１〜１００μｍの少なくとも１層の層を前処理層として堆積、拡散または含浸させることが好ましい。好適な膜厚の中間層と表面層を形成することができる。堆積、拡散及び含浸を組み合わせて順次行うことで、２層以上の前処理層を形成してもよい。前処理層は２層以上としても全体で１〜１００μｍが好ましく、より好ましくは１〜７５μｍ、さらに好ましくは１〜５０μｍである。前処理層が１μｍ未満であると、密着性向上に十分な効果がなく、１００μｍを超えると径の増加が大きくなりすぎるため、構造体としての取り扱いに支障をきたす。 Preferably, at least one layer of 1 to 100 μm is deposited, diffused or impregnated on the substrate 2 as a pretreatment layer. It is possible to form an intermediate layer and a surface layer of suitable thickness. Two or more pretreatment layers may be formed by sequentially combining deposition, diffusion and impregnation. The total number of pre-treatment layers is preferably 1 to 100 μm, more preferably 1 to 75 μm, and still more preferably 1 to 50 μm. If the pre-treatment layer is less than 1 μm, there is no sufficient effect to improve the adhesion, and if it exceeds 100 μm, the increase in diameter becomes too large, which hinders the handling as a structure.
（第２工程）
前処理層の表面を、元素Ｂ群のうちの他の少なくとも１種である元素で被覆することによって被覆層を形成する。元素Ｂ群は、例えばＦｅ、Ｎｉ、Ｐｄ、Ｂｅ、Ｍｇ、Ａｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｃｒ、Ｚｒ、Ｈｆ、Ｌａ、Ｃｅ、Ｙ、Ｓｃのうちの少なくとも１種であるが、前処理層に含ませた元素とは重複しないように選択される。例えば、元素Ｂ群のうち、Ｂｅ、Ｍｇ、Ａｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｃｒ、Ｚｒ、Ｈｆ、Ｌａ、Ｃｅ、Ｙ、Ｓｃが好ましく、より好ましくはＡｌ、Ｃｒ、Ｔｉである。これらの元素は合金化されたときに合金中に析出するセラミックスになりやすく、耐久性の向上に寄与しやすい。
(Step 2)
A covering layer is formed by covering the surface of the pretreatment layer with an element which is at least one other element of the group of elements B. The element B group is, for example, at least one of Fe, Ni, Pd, Be, Mg, Al, Si, Ca, Ti, Cr, Zr, Hf, La, Ce, Y, and Sc, but the pretreatment layer It is selected so as not to overlap with the elements contained in. For example, among the element B group, Be, Mg, Al, Si, Ca, Ti, Cr, Zr, Hf, La, Ce, Y, and Sc are preferable, and Al, Cr, and Ti are more preferable. These elements tend to be ceramics that precipitate in the alloy when they are alloyed, and tend to contribute to the improvement of the durability.
被覆層は、アルミナイズ法、クロマイズ法、又はチタナイズ法によって形成する。被覆層の厚さは１〜１００μｍが好ましく、より好ましくは１〜７５μｍ、さらに好ましくは１〜５０μｍである。被覆層が１μｍ未満であると、表面層の形成に十分な効果がなく、１００μｍを超えると径の増加が大きくなりすぎるため、構造体としての取り扱いに支障をきたす。全体の厚さが１〜１００μｍとなる範囲で２層以上の被覆層を形成してもよい。 The coating layer is formed by an aluminizing method, a chromizing method, or a titanizing method. The thickness of the coating layer is preferably 1 to 100 μm, more preferably 1 to 75 μm, and still more preferably 1 to 50 μm. If the covering layer is less than 1 μm, the effect of forming the surface layer is not sufficient. If the covering layer exceeds 100 μm, the increase in diameter becomes too large, which causes a problem in handling as a structure. Two or more coating layers may be formed within the range of the total thickness of 1 to 100 μm.
（第３工程）
次に基材１と前処理層と被覆層とを合金化させることによって、中間層３及び表面層４を形成する。具体的には、酸化性雰囲気で、加熱し、冷却する。表面層４の合金は、基材由来の元素Ａ群のうち少なくとも１種と、前処理層に由来する元素Ｂ群のうちの少なくとも１種と、被覆層に由来する元素Ｂ群のうちの他の少なくとも１種とを含む合計３種以上の元素を含む合金であり、かつ、合計３種以上の元素のひとつはクロムである。表面層２にはセラミックスが分散しており、セラミックスは、被覆層に由来する元素の酸化物である。表面層４の合金にはＣｒが必ず含まれ、前処理層に由来する元素Ｂ群は、例えば、前処理層が金属からなる場合には前処理層に由来する元素Ｂ群は１種であり、前処理層が合金からなる場合には前処理層に由来する元素Ｂ群は２種以上となる。被覆層に由来する元素Ｂ群のうちの他の少なくとも１種は、例えば、被覆層が金属からなる場合には被覆層に由来する元素Ｂ群は１種であり、被覆層が合金からなる場合には被覆層に由来する元素Ｂ群は２種以上となる。ただし、前処理層に含まれる元素と、被覆層に含まれる元素とは重複がないようにすることが好ましい。
(Third step)
Next, the intermediate layer 3 and the surface layer 4 are formed by alloying the substrate 1, the pretreatment layer and the covering layer. Specifically, heating and cooling are performed in an oxidizing atmosphere. The alloy of the surface layer 4 is at least one of the element A group derived from the base material, at least one of the element B group derived from the pretreatment layer, and the other of the element B group derived from the covering layer And an alloy containing three or more elements in total, and at least one of the three or more elements in total is chromium. Ceramics are dispersed in the surface layer 2, and the ceramic is an oxide of an element derived from the covering layer. The alloy of the surface layer 4 always contains Cr, and the element B group derived from the pretreatment layer is, for example, one element B group derived from the pretreatment layer when the pretreatment layer is made of metal. When the pretreatment layer is made of an alloy, the element B group derived from the pretreatment layer is two or more. For example, when the coating layer is made of metal, at least one other element B group derived from the coating layer is one element B group derived from the coating layer, and the coating layer is made of an alloy The element B group derived from the coating layer is two or more. However, it is preferable that the element contained in the pretreatment layer and the element contained in the covering layer do not overlap.
中間層３及び表面層４とは、別々に形成するのではなく、基材１と前処理層と被覆層とを合金化させることによって、セラミックスが分散した表面層４が形成され、同時に、中間層が析出する。そして、基材１に含まれていた元素、前処理層に含まれていた元素及び被覆層に含まれていた元素が拡散することによって、中間層３及び表面層４に所定の割合で分布する。 The intermediate layer 3 and the surface layer 4 are not separately formed, but the surface layer 4 in which the ceramic is dispersed is formed by alloying the base material 1, the pretreatment layer and the covering layer, and at the same time, the intermediate layer is formed. Layers precipitate out. Then, the element contained in the substrate 1, the element contained in the pretreatment layer, and the element contained in the covering layer are diffused to be distributed in the intermediate layer 3 and the surface layer 4 at a predetermined ratio. .
以下、実施例を示しながら本発明についてさらに詳細に説明するが、本発明は実施例に限定して解釈されない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not construed as being limited to the examples.
（実施例１）
外径３５ｍｍ、内径８ｍｍ、長さ２００ｍｍの中空管形状を有し、６６Ｃｒ‐３４Ｆｅ合金製の保護管（基材ともいう。）を準備した。保護管の表面のビッカース硬度は３８０Ｈｖであった。保護管の外周面を鏡面研磨し、アセトン中で超音波洗浄を行った。次に、Ｆｅの箔で保護管を包み、放電プラズマ焼結機を用いて加圧状態で８００℃で１時間加熱し、保護管の外周面にＦｅ含浸処理を行うことで、前処理層を形成した。図２に前処理実施後の断面ＳＥＭ画像を示す。前処理層は被膜とＦｅ拡散層からなり、その厚さの合計は３０μｍであった。ＳＥＭ−ＥＤＸでの観察によって、前処理層には基材由来のＣｒと、含侵したＦｅが含まれることが確認された。組成は、原子百分率でＣｒが２ａｔ％、Ｆｅが９８ａｔ％であった。また、基材へのＦｅの拡散も確認された（Ｆｅ拡散層）。次に、前処理層の表面に被覆層として厚さ５０μｍのＡｌ層を形成した。被覆層はカロライズ法によって形成した。次に、基材であるＣｒ合金の保護管と鉄を含む前処理層とアルミニウムの被覆層とを合金化させた。酸化性雰囲気で、加熱し、冷却した。合金化させることによって、基材側中間層３ａ、表面層側中間層３ｂ及び表面層４が形成された。図３に表面層形成後の断面ＳＥＭ画像を、図４に表面層形成後の断面における組成分布グラフを、表１に各層の組成を示す。また、表面層４ではセラミックス粒子と合金相が観察された。セラミックス粒子と合金相の組成を表２に示す。
Example 1
A 66Cr-34Fe alloy protective tube (also referred to as a base material) having an outer diameter of 35 mm, an inner diameter of 8 mm, and a length of 200 mm was prepared. The Vickers hardness of the surface of the protective tube was 380 Hv. The outer peripheral surface of the protective tube was mirror-polished and subjected to ultrasonic cleaning in acetone. Next, wrap the protective tube with Fe foil and heat it at 800 ° C. for 1 hour in a pressurized state using a spark plasma sintering machine to carry out Fe impregnation treatment on the outer peripheral surface of the protective tube, thereby pretreating the layer. It formed. The cross-sectional SEM image after pre-processing implementation is shown in FIG. The pretreatment layer consisted of a film and an Fe diffusion layer, and the total thickness thereof was 30 μm. The observation with SEM-EDX confirmed that the pretreatment layer contains Cr derived from the base material and impregnated Fe. The composition was 2 at% of Cr and 98 at% of Fe in atomic percentage. In addition, the diffusion of Fe into the substrate was also confirmed (Fe diffusion layer). Next, a 50 μm thick Al layer was formed on the surface of the pretreatment layer as a covering layer. The covering layer was formed by the carolization method. Next, the protective tube of Cr alloy which is a base material, the pretreatment layer containing iron, and the coating layer of aluminum were alloyed. Heat and cool in an oxidizing atmosphere. By alloying, the base material side intermediate layer 3a, the surface layer side intermediate layer 3b and the surface layer 4 were formed. FIG. 3 shows a cross-sectional SEM image after formation of the surface layer, FIG. 4 shows a composition distribution graph in a cross section after formation of the surface layer, and Table 1 shows the composition of each layer. In the surface layer 4, ceramic particles and an alloy phase were observed. The compositions of the ceramic particles and the alloy phase are shown in Table 2.
表面層４のビッカース硬度は６９３Ｈｖであり、基材の表面硬度よりも高かった。表面層４のセラミックス粒子の粒径は、ほぼ揃っており、１μｍ未満の粒子や２０μｍを超える粒子も存在していたものの、それらの数は少なく、ほとんどの粒子が１〜２０μｍの大きさで分布していた。すなわち、走査型電子顕微鏡で倍率１０００倍で観察した画像観察において認識できる粒子のうち、粒径が１〜２０μｍの範囲にあるセラミックス粒子が、表面に垂直な断面において、面積比で４０％以上を占めていた。表面層４の合金Ｘは、Ａｌ‐Ｆｅ‐Ｃｒ合金であり、セラミックスはアルミナ粒子であった。アルミナ粒子は、表面層４のみに存在した。表面層４において、セラミックスが占める割合は４８．７１％であった。なお測定は粒径測定ソフト（株式会社イノテック社製、Ｑｕｉｃｋ Ｇｒａｉｎ）を使用し、測定したい粒とそうでない部分とを２値化によって明暗に分け、明の部分を計測した。なお、セラミックスの面積比の算出は、粒径１〜２０μｍのセラミックス粒子のみを用いて算出した。粒径１μｍ未満の微細粒子は面積への影響が小さいこと及び測定が難しいことから除外した。基材側中間層３ａは基材２と表面層側中間層３ｂとの間の組成を有していた。基材側中間層３ａには、Ｃｒ、Ａｌ、Ｆｅが含まれていた。表面層側中間層３ｂは均一組成層であった。層内でブレが±１０％以内に収まっていた。 The Vickers hardness of the surface layer 4 was 693 Hv, which was higher than the surface hardness of the substrate. The particle size of the ceramic particles in the surface layer 4 is almost uniform, and although particles smaller than 1 μm and particles larger than 20 μm are also present, their number is small and most particles are distributed in a size of 1 to 20 μm Was. That is, among particles that can be recognized in image observation observed at a magnification of 1000 times with a scanning electron microscope, ceramic particles having a particle diameter in the range of 1 to 20 μm have an area ratio of 40% or more in a cross section perpendicular to the surface. It occupied. The alloy X of the surface layer 4 was an Al-Fe-Cr alloy, and the ceramic was alumina particles. Alumina particles were present only in the surface layer 4. The proportion of the ceramic in the surface layer 4 was 48.71%. The measurement was carried out using a particle size measurement software (Quick Grain, manufactured by Inotech Co., Ltd.), the particles to be measured and the portions not to be measured were divided into bright and dark portions by binarization, and the bright portions were measured. In addition, calculation of the area ratio of ceramics was computed using only the ceramic particle of 1 to 20 micrometers of particle sizes. Fine particles having a particle size of less than 1 μm were excluded because they have a small effect on the area and are difficult to measure. The substrate side intermediate layer 3a had a composition between the substrate 2 and the surface layer side intermediate layer 3b. The base material side intermediate layer 3 a contained Cr, Al, and Fe. The surface layer side intermediate layer 3b was a uniform composition layer. The blur was within ± 10% in the layer.
（実施例２）
実施例１と同じ保護管を準備した。次に、Ｆｅメッキ液を用いて、電解メッキ法によって、前処理層として厚さ１５μｍのＦｅ被膜を形成した。図５に前処理実施後の断面ＳＥＭ画像を示す。ＳＥＭ−ＥＤＸでの観察によって、前処理層にはメッキ膜のＦｅのみ含まれることが確認された。次に、前処理層の表面に被覆層として厚さ５０μｍのＡｌ層を形成した。被覆層はカロライズ法によって形成した。次に、基材であるＣｒ合金の保護管と鉄を含む前処理層とアルミニウムの被覆層とを合金化させた。酸化性雰囲気で、加熱し、冷却した。合金化させることによって、基材側中間層３ａ、表面層側中間層３ｂ及び表面層４が形成された。図６に表面層形成後の断面ＳＥＭ画像を、図７に表面層形成後の断面における組成分布グラフを、表３に各層の組成を示す。また、表面層４ではセラミックス粒子と合金相が観察された。セラミックス粒子と合金相の組成を表４に示す。
(Example 2)
The same protective tube as in Example 1 was prepared. Next, an Fe plating solution was used to form a 15 μm thick Fe film as a pretreatment layer by electrolytic plating. The cross-sectional SEM image after pre-processing implementation is shown in FIG. Observation with SEM-EDX confirmed that the pre-treatment layer contained only Fe of the plated film. Next, a 50 μm thick Al layer was formed on the surface of the pretreatment layer as a covering layer. The covering layer was formed by the carolization method. Next, the protective tube of Cr alloy which is a base material, the pretreatment layer containing iron, and the coating layer of aluminum were alloyed. Heat and cool in an oxidizing atmosphere. By alloying, the base material side intermediate layer 3a, the surface layer side intermediate layer 3b and the surface layer 4 were formed. FIG. 6 shows a cross-sectional SEM image after formation of the surface layer, FIG. 7 shows a composition distribution graph in a cross section after formation of the surface layer, and Table 3 shows the composition of each layer. In the surface layer 4, ceramic particles and an alloy phase were observed. The compositions of the ceramic particles and the alloy phase are shown in Table 4.
表面層４のビッカース硬度は６４５Ｈｖであり、基材の表面硬度よりも高かった。表面層４のセラミックス粒子の粒径は、ほぼ揃っており、１μｍ未満の粒子や２０μｍを超える粒子も存在していたものの、それらの数は少なく、ほとんどの粒子が１〜２０μｍの大きさで分布していた。すなわち、走査型電子顕微鏡で倍率１０００倍で観察した画像観察において認識できる粒子のうち、粒径が１〜２０μｍの範囲にあるセラミックス粒子が、表面に垂直な断面において、面積比で４０％以上を占めていた。表面層４の合金Ｘは、Ａｌ‐Ｆｅ‐Ｃｒ合金であり、セラミックスはアルミナ粒子であった。アルミナ粒子は、表面層４のみに存在した。表面層４において、セラミックスが占める割合は５０．５８％であった。なお測定は粒径測定ソフトを使用し、測定したい粒とそうでない部分とを２値化によって明暗に分け、明の部分を計測した。なお、セラミックスの面積比の算出は、粒径１〜２０μｍのセラミックス粒子のみを用いて算出した。粒径１μｍ未満の微細粒子は面積への影響が小さいこと及び測定が難しいことから除外した。基材側中間層３ａは傾斜組成を有し、基材側中間層３ａ内において基材２から表面層側中間層３ｂへ向かって、Ｃｒ「多」からＣｒ「少」に組成が変化した。また、基材側中間層３ａ内において基材２から表面層側中間層３ｂへ向かって、Ａｌ「少」からＡｌ「多」に組成が変化した。また、基材側中間層３ａ内において基材２から表面層側中間層３ｂへ向かって、Ｆｅ「少」からＦｅ「多」に組成が変化した。基材側中間層３ａには、Ｃｒ、Ａｌ、Ｆｅが含まれていた。表面層側中間層３ｂは均一組成層であった。層内でブレが±１０％以内に収まっていた。 The Vickers hardness of the surface layer 4 was 645 Hv, which was higher than the surface hardness of the substrate. The particle size of the ceramic particles in the surface layer 4 is almost uniform, and although particles smaller than 1 μm and particles larger than 20 μm are also present, their number is small and most particles are distributed in a size of 1 to 20 μm Was. That is, among particles that can be recognized in image observation observed at a magnification of 1000 times with a scanning electron microscope, ceramic particles having a particle diameter in the range of 1 to 20 μm have an area ratio of 40% or more in a cross section perpendicular to the surface. It occupied. The alloy X of the surface layer 4 was an Al-Fe-Cr alloy, and the ceramic was alumina particles. Alumina particles were present only in the surface layer 4. The proportion of the ceramic in the surface layer 4 was 50.58%. The measurement was performed using a particle size measurement software, the particles to be measured and the non-particles were divided into bright and dark portions by binarization, and the bright portions were measured. In addition, calculation of the area ratio of ceramics was computed using only the ceramic particle of 1 to 20 micrometers of particle sizes. Fine particles having a particle size of less than 1 μm were excluded because they have a small effect on the area and are difficult to measure. The substrate side intermediate layer 3a has a graded composition, and the composition changes from Cr "large" to Cr "small" from the substrate 2 toward the surface layer side intermediate layer 3b in the substrate side intermediate layer 3a. Moreover, in the base material side intermediate layer 3a, the composition changed from Al “small” to Al “many” from the base material 2 to the surface layer side intermediate layer 3b. In addition, in the base material side intermediate layer 3a, the composition changed from Fe "small" to Fe "many" from the base material 2 to the surface layer side intermediate layer 3b. The base material side intermediate layer 3 a contained Cr, Al, and Fe. The surface layer side intermediate layer 3b was a uniform composition layer. The blur was within ± 10% in the layer.
１ 焼却炉用熱電対の保護管用構造体
２ 基材
３ 中間層
３ａ 基材側中間層
３ｂ 表面層側中間層
４ 表面層
1 Structure for protective tube of thermocouple for incinerator 2 Base material 3 Intermediate layer 3a Intermediate layer side intermediate layer 3b Surface layer side intermediate layer 4 Surface layer
Claims (14)
前記基材は、クロム又はクロム合金と不可避不純物とからなり、
前記表面層は、前記基材に含まれる元素Ａ群のうち少なくとも１種と、元素Ｂ群のうち少なくとも２種とを含む合計３種以上の元素を含む合金からなり、合計３種以上の元素のひとつはクロムであり、かつ、前記表面層は、前記合金からなる相に前記Ｂ群元素のうち１種の元素の酸化物であるセラミックスが分散している組織を有していることを特徴とする焼却炉用熱電対の保護管用構造体。 A substrate having the shape of a protective tube of an incinerator thermocouple, at least two or more intermediate layers bonded to at least the surface side surface of the substrate, and a surface bonded to the surface of the intermediate layer A protective tube structure for a thermocouple for an incinerator having a layer;
The substrate is made of chromium or chromium alloy and unavoidable impurities.
The surface layer is made of an alloy containing three or more elements in total including at least one of elements A group contained in the base material and at least two of elements B group, and a total of three or more elements in total Is one of chromium, and the surface layer has a structure in which a ceramic which is an oxide of one of the elements of the group B element is dispersed in the phase made of the alloy The structure for the protective tube of the incinerator thermocouple.
クロム又はクロム合金と不可避不純物とからなる基材の表面に、堆積、拡散又は含浸によって元素Ｂ群のうちの少なくとも１種を含む前処理層を形成する第１工程と、
前記前処理層の表面を、元素Ｂ群のうちの他の少なくとも１種である元素で被覆することによって被覆層を形成する第２工程と、
前記基材と前記前処理層と前記被覆層とを合金化させることによって、前記中間層及び前記表面層を形成する第３工程と、を有し、
前記表面層の合金は、前記基材由来の元素Ａ群のうち少なくとも１種と、前記前処理層に由来する元素Ｂ群のうちの少なくとも１種と、前記被覆層に由来する元素Ｂ群のうちの他の少なくとも１種とを含む合計３種以上の元素を含む合金であり、かつ、合計３種以上の元素のひとつはクロムであり、
前記表面層にはセラミックスが分散しており、
前記セラミックスは、前記被覆層に由来する元素の酸化物であることを特徴とする焼却炉用熱電対の保護管用構造体の製造方法。 A method of manufacturing a protective tube structure for a thermocouple for an incinerator according to any one of claims 1 to 10,
A first step of forming a pretreatment layer containing at least one element of Group B by deposition, diffusion or impregnation on the surface of a substrate comprising chromium or a chromium alloy and an unavoidable impurity;
A second step of forming a covering layer by covering the surface of the pretreatment layer with at least one other element of the group of elements B;
And a third step of forming the intermediate layer and the surface layer by alloying the base material, the pretreatment layer, and the covering layer,
The alloy of the surface layer is at least one of the group of elements A derived from the base, at least one of the group of elements B derived from the pretreatment layer, and the group of elements B derived from the covering layer An alloy containing a total of three or more elements including at least one other element, and one of the three or more elements in total is chromium;
Ceramics are dispersed in the surface layer,
The method for manufacturing a protective tube structure for a thermocouple for an incinerator, wherein the ceramic is an oxide of an element derived from the covering layer.
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