JPS6144153A - Manufacture of alloy superior in strength and corrosion resistance - Google Patents

Abstract

PURPOSE:To obtain an alloy superior in mechanical strength and corrosion resistance, by cooling rapidly at a specified rate from molten state, an Fe base alloy contg. respectively prescribed ratios of N, Cr or/and Mo, and >= one kind among S, C, Si, P, and solidifying it. CONSTITUTION:The Fe-base alloy contg. by atomic %, 0.01-20 N, 1-40 Cr or/ and Mo, 7-30 one kind or more of B, C, Si and P being semimetal element, further 0.1-15 the following secondary elements is prepared. Said secondary element is >=one kind among Ti, Zr, V, Nb, W, Mo, Mn, Cu, Ag, Al. Next, the Fe base alloy is cooled rapidly from molten state to 300 deg.C at >=1,000 deg.C/sec rate and solidified. As the result, alloy favorable as a material used for apparatus, industrial chemical plant, operated in air, sea water or oxidizing atmosphere, etc. and especially required with resistances for general corrosion, stress corrosion, pitting corrosion, etc. is obtd.

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明に機織的強１止、１１食性にすぐれた合金のトメ
造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for making an alloy with excellent mechanical strength and corrosion resistance.

（従来のＪ支９Ｎ） 」！近５月１−１の耐食性にたいする〃求が苛０，１：
こなり、従来の材、ド１では使用に耐えない場合が多く
なっている。この観点で、たとえば日本金属学会＝ご和
４９年春期（第７４回）大会に発〒〈された非ｉム質鉄
・クロム系合金Ｖｉ３原子係以上のクロムの゛骨加で−
すぐれた耐食性を示すと客れている。ｉ−：“１ｆＩＨ
４ｉ＋１３４９−９１０１４号によれｄ　Ｆｅ（（１＋
Ｉｌ　、ｓ　？＋＋　３．Ａｔ２　。(Conventional J support 9N)”! High demand for corrosion resistance in May 1-1:
As a result, there are many cases where conventional materials, such as DO1, cannot withstand use. From this point of view, for example, the study presented at the 74th spring meeting of the Japan Institute of Metals (Japan Institute of Metals):
It is praised for its excellent corrosion resistance. i-: “1fIH
According to No. 4i+1349-91014, d Fe((1+
Il,s? ++ 3. At2.

Ｃｒ？８Ｐ、、　Ｂ、ｌｉ；＋、などの組成と持つ非、
；＾（ｑ合］’ｉ、　７．ｒ　ｈ、”　：”＋酸などに
対して耐食性がよいことが記、ｌ・Ｍ　Ｊれて′ハる。Cr? 8P,, B, li;+, etc. and non-,
;^(q)'i, 7.r h, ":"+ It is noted that it has good corrosion resistance against acids, etc.

（発明が解決しようとする問題点） これらの非晶質合金は、従来の結晶性合金とくらべて特
異な性質を示すことで注目すべきであるが、すべての非
晶質合金がすぐれた耐食性を示すわけではない。たとえ
ば日本金属学会１ＯＪＤ４を正度春期（第７４回）大会
Ｅｌ’）演概要１８８頁によｉｔば、Ｆｅ−Ｐ−Ｃ非晶
質合金およびｉＪｌ；）の低いＦＩ！−：１ｌ−ｐ−ｃ
非晶質合金はＩＭＨ２Ｓｏ、及び■゛シＮｌＩＣノ’＋
ｊ：Ｉ’を千では活性１１Ｌ位域で試料が消失すると記
、１父されている。(Problem to be Solved by the Invention) These amorphous alloys are noteworthy for exhibiting unique properties compared to conventional crystalline alloys, but all amorphous alloys have excellent corrosion resistance. It does not indicate that For example, according to page 188 of the presentation summary of the Japan Institute of Metals 1OJD4 Seido Spring (74th) Conference El'), it states that Fe-P-C amorphous alloys and iJl;) have low FI! -:1l-p-c
The amorphous alloy is IMH2So, and
It has been written that the sample disappears in the active 11L region when j:I' is 1,000.

本発明者らｄ非晶Ｔｔ　ｋふくむ、急冷ｙｔ周合金のと
くに強度と耐食１１（て注目して５Ｉ細なａ）Ｉ究を行
った。The present inventors conducted a detailed investigation focusing on the strength and corrosion resistance of quenched yt peripheral alloys, including d amorphous Tt k.

こ５で非晶質合金とは、東予配列が長距−（ｔの規則的
な周期性を持たない合金で、通常の、く腺回折まだは電
子線回折によって結晶ンこ特有な回折１夕を示４ず、液
体に似たハローパターンを示す状態のものをいう。本発
明者らの研究の結果、従来発表されている非晶質合金の
４１食性は成分系によって異なること、！たもつともよ
い耐食性を示す鉄　クロム系非晶質合金は常温で使用す
る場合にけ１酵、硫酸、硝酸などの環境中ですぐれだ耐
食性を示すが、たとえば８０℃に加熱した硫酸ｊ谷液中
というような苛酷な腐食環境中では腐食が著しく、到底
実用に、ｔｆえないことを見出した。そこで本発明者ら
はか＼る問題の解決の研究を裟意進めた結果、上記の欠
点を除去する新合金の製法に成功した。In this case, an amorphous alloy is an alloy in which the Toyo alignment does not have a regular periodicity of long distance - It refers to a state in which a halo pattern resembling that of a liquid is exhibited without showing 41.As a result of the research conducted by the present inventors, it was found that the erodibility of the previously published amorphous alloys differs depending on the component system! Iron chromium-based amorphous alloys exhibit excellent corrosion resistance when used at room temperature in environments such as fermentation, sulfuric acid, and nitric acid. The inventors of the present invention have found that the corrosion is so severe in such a severe corrosive environment that it cannot be put to practical use.As a result, the inventors of the present invention have diligently conducted research to solve this problem, and as a result, the above-mentioned drawbacks have been eliminated. Succeeded in producing a new alloy.

（間頂点を解決するだめの手段） すなわち本発明はＮを０．０１〜２０原子％、Ｃｒおよ
びＭＯの１種捷たは２種を１〜４０原子係、半金属元素
としてＢ、Ｃ，Ｓｉ　　およびＰの１種またＶｉ２種以
上を総和で７〜３０原子係含み、甘たけさらにこれらに
ＴＩ、　　Ｚｒ、　ｖ、１４ｂ、　Ｗ、　Ｍｎ、Ｃｕ。(Another means to solve the problem) That is, the present invention includes 0.01 to 20 atomic % of N, 1 to 40 atomic % of one or both of Cr and MO, B, C, It contains one type of Si and P or two or more types of Vi in a total of 7 to 30 atoms, and in addition to these, TI, Zr, V, 14b, W, Mn, and Cu.

Ａｌ　、八ｔの１種または２１！ＩＩ以上を籠、和でＯ
，１〜１５原子係含有し、残ｆｉＢがＦｅおよび不町炭
不純物よりなる合金を熔融状態から３００’Ｃまで１０
００℃／秒以上の冷却速度で急冷鑓固させることを特徴
とする強度および耐食性のすぐれた合金の製造方法を要
旨とするものである。Al, 8t type 1 or 21! Cage II and above, O in sum
, 1 to 15 atoms, and the remaining fiB consists of Fe and uncharted coal impurities from a molten state to 300'C for 10
The gist of this invention is a method for producing an alloy with excellent strength and corrosion resistance, which is characterized by rapid cooling and solidification at a cooling rate of 00° C./second or higher.

次に本発明における各種元素のｂＫ分句囲及び冷却速度
の限定理由について述べる。Next, the reasons for limiting the bK range and cooling rate of various elements in the present invention will be described.

まず＋４けＣｒあるいはＭｏとの共存下で副食性を改善
する効果をもち、本発明のもつとも特徴とするところで
ある。その添加範囲は００１係以下では耐食性を改善す
る効果が殆どなくなり、また２原子チ以上は工業的に添
加することが困難なのでそれぞれ添加量の上、下限をも
うけた。First, it has the effect of improving side food properties in the coexistence with +4 Cr or Mo, which is another feature of the present invention. If the addition range is less than 001, the effect of improving corrosion resistance is almost lost, and if it is more than 2 atoms, it is difficult to add it industrially, so upper and lower limits were set for each addition amount.

Ｃｒ、み・よびＭｏは【Ｉの共存下でとくに４１食性を
改善するのに効果があり、また強度をｒａ加させる元素
であるが、１チ以下ではその効果が少なく、壕だ４０原
子係以上では脆化をおこして合金の製造が１、Ｉ　Ｌ・
ｌｔになるのでそれぞれ限界をもうけた。半金属元素は
合金ｆ：熔融状態から急冷した場合に、延咀靭性などの
磯城的性質を安定にするだめの必須成すである。そのた
めに総和で７チ以上は必要であるが、３０幅以上では脆
化を生ずるのでそれぞれ上、下限とした。Cr, Mo, and Mo are elements that are particularly effective in improving 41 eating habits in the coexistence of [I, and are also elements that add strength to ra, but their effect is small below 1 t, and the 40 atomic ratio is In the above case, embrittlement occurs and the production of the alloy is 1, IL・
Since it will be LT, each has its limits. The semimetallic element is an essential component for stabilizing Iso-like properties such as ductile toughness when the alloy f: is rapidly cooled from a molten state. For this purpose, a total width of 7 or more is required, but a width of 30 or more causes embrittlement, so the upper and lower limits were set respectively.

次に副次的に添加されるＴｉ　、　　計、ｌ／、Ｎｂ。Next, Ti, total, l/, Nb is added as a subsidiary.

＋Ｖ、　ｕｎ、　Ｃｕ、　ＡＩ、　ｒ＼Ｃは合金の衷造
芥易化、強；仄の増加、熱的安定性の改善あるいはさら
に磁性材（−［としてｈａ気気持特性改善のために添加
されるものである。その添加範囲はｏ１原子チ以下では
・ｉＧ　Ｊｌｐ元素の効果が少く、また１５ｃＩＩ以上
では合金装造が困り１ｔになるのでそれぞれ上下限とし
た。+V, un, Cu, AI, r\C are added to make the alloy easier to build, increase strength, increase thermal stability, or further improve the magnetic material (-[ha) to improve the air-feeling properties. The range of its addition is set at upper and lower limits, respectively, since the effects of the iG, Jlp elements are small below 1 atom, and above 15cII, it is difficult to form the alloy and it becomes 1t.

本発明方法により製造された合金は熔融状態から急冷し
て非晶質状態とした時にもつとも耐食性がよいが、結晶
ｒＪＩＩ状ｊ、ｉｙが混在した場合、ちるいは執処理に
よって結晶化が１１（行した状態でも、：％強度ス・・
よび晶ｉ１食性を示す。しかしながら熔融状態からの冷
却速度かがすき゛ると成分の不均一なａｌ織になり、機
織的性Ｔ〔も・１更安定になるので、姑１融状聾から、
原子の拡散が不活発となる３００℃１でつ冷却速度を１
０００℃／秒以上にする必要が、ｒｐ）る。The alloy produced by the method of the present invention has good corrosion resistance even when it is rapidly cooled from a molten state to an amorphous state. However, when crystals rJII-like j, iy are mixed, crystallization may occur due to oxidation treatment. Even in the state of % strength...
It exhibits a monophagous diet. However, if the cooling rate from the molten state is too fast, the composition becomes uneven and the weaving property T becomes even more stable.
The cooling rate is 1 at 300℃, where atomic diffusion becomes inactive.
It is necessary to increase the temperature to 000°C/sec or higher.

次に本発明の実施例を示す。Next, examples of the present invention will be shown.

（実洲例） 第１表に示す組成の合金を、直径が０４ｆｆ１のノズル
を持つ石英るつ１１内で熔解し、１０００ないし５００
０　ｒ、ｐ、ｍ　　の速度で回転する・１鷺製ドラムの
内面に噴射して、色、冷、疑問させた。拭榊は巾１〜３
宵１、厚さ１０〜１００μ口のリボン状で、冷却速度は
ドラムの回転数、”ｊ１射速度、試料厚きなどによって
変るが約５　Ｘ　１０３℃／秒からＩ　Ｘ　ｌ　ｏ’ｃ
／秒の間で変化きせた。まだ一部の試ｒ４は％１表内に
示す熱処理を行って結晶化を進行させた。強度はマイク
ロビッカースかたさでｌ１１＋１定し、耐食性試験は８
０℃の５％Ｈ，ＳＯ，に６時間ｄびｉして、腐食減最の
測定から吉１食性を判定した。また非晶質あるいは結晶
′ＩＩＴの、１ｊｌｌ定は通常のχ、？）１回折を行な
い、ハローパターンの回折線がイ４）られた場合には非
晶質であると判定した。(Actual example) An alloy having the composition shown in Table 1 is melted in a quartz crucible 11 having a nozzle with a diameter of 04ff1.
It was sprayed onto the inner surface of a 1-Sagi drum rotating at a speed of 0 r, p, m to make it color, cool, and questionable. Width 1-3
Evening 1: It is in the form of a ribbon with a thickness of 10 to 100μ, and the cooling rate varies depending on the number of rotations of the drum, the injection speed, the thickness of the sample, etc., but it ranges from about 5 × 103 °C/sec to I × l o'c.
It changed within / seconds. Some samples of sample r4 were subjected to the heat treatment shown in the %1 table to promote crystallization. Strength is determined by micro-Vickers hardness as l11+1, and corrosion resistance test is 8
After dipping in 5% H, SO at 0°C for 6 hours, corrosion resistance was determined by measuring the maximum corrosion reduction. Also, the 1jll constant of amorphous or crystalline 'IIT is the usual χ,? ) 1 diffraction was performed, and if a halo pattern of diffraction lines was observed, it was determined that the material was amorphous.

”ｊ；　１表のデータかられかるように、本発明方法に
より製造された合金は既知の合金にくらべて強度が、−
’５　＜　、　４１食性もきわめてすぐれている。"j; As can be seen from the data in Table 1, the alloy produced by the method of the present invention has -
'5 <, 41 Eating habits are also extremely good.

なお、本発明の実抛例においては熔融合金を遠・し・・
＋）遺失してより製造したリボノ状のものを示したが、
本発明方法は丈δ融状態から圧延方式によっても、１だ
熔融状態からの噴射急冷方式あるいは１急速し之債法に
より他の材料表面に被覆することも可能である。したが
って形状もリボン状に限らず、箔状、粉状、粉末状、あ
るいは異独材料の被覆材として使用することも可能であ
る。In addition, in the practical example of the present invention, the molten alloy is avoided...
+) I showed a ribono-shaped item that was lost and manufactured,
In the method of the present invention, it is also possible to coat the surface of other materials by rolling from a molten state, by jet quenching from a molten state, or by a rapid cooling method. Therefore, the shape is not limited to the ribbon shape, but it can also be used in the form of foil, powder, powder, or as a covering material for different materials.

又、本発【先方法により′Ｍ潰された合金において特筆
すべきことは高強度で、かつ耐食性に優れていることを
利用し、大気中、海水中、あるいは酸化雰囲気中等で使
用される装置、化学工業プラント等、特に−１全面腐食
、耐応力腐食、耐孔食性等を一′〃求でれる場合に使用
する材料として好適でチロ。In addition, the special feature of the alloy crushed by the above method is its high strength and excellent corrosion resistance. It is suitable as a material for use in chemical industry plants, etc., where -1 general corrosion resistance, stress corrosion resistance, pitting corrosion resistance, etc. are required.

また種々の材料表面に噴射またｌ−ｉ被覆することＫよ
り（ｊ＾洋構造物、表面処理鋼板等に使用することがで
きる等その効果、応用範囲は極めて大きい。In addition, it can be used for spraying or l-i coating on the surfaces of various materials, such as structures, surface-treated steel plates, etc., and its effects and range of applications are extremely large.

Claims (1)

【特許請求の範囲】[Claims] Ｎを０．０１〜２．０原子％、ＣｒおよびＭｏの１種ま
たは２種を１〜４０原子％、半金属元素としてＢ、Ｃ、
ＳｉおよびＰの１種または２種以上を総和で７〜３０原
子％含み、またはさらにこれらにＴｉ、Ｚｒ、Ｖ、Ｎｂ
、Ｗ、Ｍｎ、Ｃｕ、Ａｇ、Ａｌの１種または２種以上を
総和で０．１〜１５原子％含有し、残部がＦｅおよび不
可避不純物よりなる合金を溶融状態から３００℃まで１
０００℃／秒以上の冷却速度で急冷凝固させることを特
徴とする強度および耐食性のすぐれた合金の製造方法0.01 to 2.0 at% of N, 1 to 40 at% of one or both of Cr and Mo, B, C, as metalloid elements,
Contains a total of 7 to 30 at% of one or more of Si and P, or further contains Ti, Zr, V, Nb
, W, Mn, Cu, Ag, and Al, in a total of 0.1 to 15 atomic %, and the balance is Fe and unavoidable impurities.
A method for producing an alloy with excellent strength and corrosion resistance, characterized by rapid solidification at a cooling rate of 000°C/second or more