TWI568861B - Low thermal expansion casting alloy and its manufacturing method - Google Patents
Low thermal expansion casting alloy and its manufacturing method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/001—Heat treatment of ferrous alloys containing Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/007—Heat treatment of ferrous alloys containing Co
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
- C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
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Description
本發明係關於例如適於半導體製造裝置等超精密機器構件、熱膨脹極小之低熱膨脹鑄造合金及其製造方法。 The present invention relates to, for example, an ultra-precision machine member suitable for a semiconductor manufacturing apparatus, a low thermal expansion casting alloy having a small thermal expansion, and a method of manufacturing the same.
過去以來，為維持、提高超精密機器之精度，而使用低熱膨脹合金，其中，32%Ni-5%Co-其餘為Fe之合金(以下稱為超恆範鋼(super invar))之在室溫附近之熱膨脹係數為1×10-6/℃以下，壓延材或鍛造材(以下稱為鋼材)已商品化且已有市售(例如非專利文獻1)。 In the past, in order to maintain and improve the precision of ultra-precision machines, low thermal expansion alloys were used, of which 32% Ni-5% Co-the rest of the alloy of Fe (hereinafter referred to as super invar) The coefficient of thermal expansion in the vicinity of the temperature is 1 × 10 -6 /° C or less, and a rolled material or a forged material (hereinafter referred to as a steel material) is commercially available and commercially available (for example, Non-Patent Document 1).
且，專利文獻1中提案以重量%計由含C：0.1%以下、Ni：30~34%、Co：4~6%之鐵基合金所成，含有Mn：0.1~1.0%與S：0.02~0.15%，並且Mn/54.94>S/32.06之快削性低熱膨脹鑄物用合金。 Further, in Patent Document 1, it is proposed to be composed of an iron-based alloy containing C: 0.1% or less, Ni: 30 to 34%, and Co: 4 to 6% by weight, and contains Mn: 0.1 to 1.0% and S: 0.02. ~0.15%, and Mn/54.94>S/32.06 fast-cutting low thermal expansion casting alloy.
另一方面，專利文獻2及專利文獻3中記載於微波導波管之共振器及半導體液浸曝光裝置之晶圓台中使用各熱膨脹係數為0.5×10-6/℃之超恆範鋼。 On the other hand, in Patent Document 2 and Patent Document 3, superconstant steels each having a thermal expansion coefficient of 0.5 × 10 -6 /° C are used in a resonator of a microwave waveguide and a wafer stage of a semiconductor liquid immersion exposure apparatus.
專利文獻1：日本特開2002-206142號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-206142
專利文獻2：日本特開2010-206615號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-206615
專利文獻3：日本特開2005-183416號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-183416
非專利文獻1：不二越股份有限公司，技術資料，[平成26年3月7日檢索]，Internet〈URL：HTTP：//www.nachi-fujikoshi.co.jp/kou/fm_alloy/fm_alloy_exeo.pdf〉 Non-Patent Document 1: Fujitsu Co., Ltd., Technical Information, [Search on March 7, 26], Internet <URL: http://www.nachi-fujikoshi.co.jp/kou/fm_alloy/fm_alloy_exeo.pdf>
不過，上述超恆範鋼鋼材為了確實獲得1×10-6/℃以下之熱膨脹係數，需將C抑制在0.02%以下之雜質等級。依據本發明者之見解，如此低C的超恆範鋼進行大氣溶解而鑄造時，多會產生氣體缺陷，工業上製造非常困難，故必須進行真空溶解。對一般之鑄造業者而言，使用昂貴的設備進行複雜之操作並不現實，製造低C之超恆範鋼鑄造品事實上並不可能。 However, in order to obtain a thermal expansion coefficient of 1 × 10 -6 /°C or less, the above-mentioned super-constant steel steel needs to suppress C to an impurity level of 0.02% or less. According to the findings of the present inventors, when such a low C super-constant steel is subjected to atmospheric dissolution and casting, gas defects are often generated, and industrial production is extremely difficult, so vacuum dissolution is necessary. For the average foundry, it is not realistic to use expensive equipment for complex operations. It is virtually impossible to manufacture a low C super-constant steel casting.
另一方面，專利文獻1之低熱膨脹鑄物用合金，Ni含量及Co含量與超恆範鋼相同，C之含量雖容許至0.1%以下之大氣可鑄造之範圍，但實施例中僅揭示C含量為0.008~0.011%之極低合金，如此極低C含量不過是顯示熱膨脹係數為0.773×10-6/℃以下。亦即，專利文獻 1中亦教示為了獲得1×10-6/℃以下之熱膨脹係數必須將C設為0.01%左右之極低值。因此，專利文獻1雖有記載可獲得適於製造薄壁大型鑄造物之合金，但實際上由於有必要降低C含量，故認為仍非常難進行大氣溶解‧鑄造，一般之鑄造業者難以使用專利文獻1之技術工業上利用鑄造合金。 On the other hand, in the alloy for low thermal expansion casting of Patent Document 1, the Ni content and the Co content are the same as those of the ultra-constant steel, and the content of C is allowed to be in the range of atmospheric castable of 0.1% or less, but only C is disclosed in the examples. The extremely low alloy content of 0.008 to 0.011%, such that the extremely low C content merely shows a coefficient of thermal expansion of 0.773 × 10 -6 / ° C or less. That is, Patent Document 1 also teaches that C must be set to an extremely low value of about 0.01% in order to obtain a thermal expansion coefficient of 1 × 10 -6 /°C or less. Therefore, Patent Document 1 describes that an alloy suitable for producing a thin-walled large-sized cast product can be obtained. However, since it is necessary to reduce the C content, it is considered that it is still very difficult to perform atmospheric dissolution and casting. It is difficult for a general foundry to use the patent literature. The technical industry utilizes a cast alloy.
且，非專利文獻1中所示之超恆範鋼鋼材僅適用於板材或棒材等單純形狀，精密裝置中使用之複雜形狀品或大型零件有必要藉切削加工或熔接組裝而製作，但超恆範鋼之被切削性及熔接性低，故亦有需要較多工數‧費用之問題。 Further, the ultra-constant steel steel material shown in Non-Patent Document 1 is only suitable for a simple shape such as a plate material or a bar material, and a complicated shape product or a large-sized component used in a precision device needs to be produced by cutting or welding assembly, but super Hengfan Steel has low machinability and weldability, so it also requires more work and expenses.
專利文獻1中係藉由添加特定量之S及Mn之基質中之MnS以改善被切削性而解決該問題，但如上述，專利文獻1之合金為了成為1×10-6/℃以下之低熱膨脹係數亦有必要使C成為0.01%左右之極低值，由於大氣鑄造困難，故實際上無法適用於複雜形狀品或大型零件，並非可本質解決該問題者。 In Patent Document 1, the problem is solved by adding a specific amount of MnS in a matrix of S and Mn to improve the machinability. However, as described above, the alloy of Patent Document 1 has a low temperature of 1 × 10 -6 /° C. or less. It is also necessary to make C a very low value of about 0.01% due to the coefficient of thermal expansion. Since it is difficult to cast in the atmosphere, it is practically impossible to apply to complicated shapes or large parts, and it is not essential to solve the problem.
因此，本發明之目的係提供一種一方面含有通常可大氣溶解及大氣鑄造之等級之C，一方面具有與超恆範鋼同等之極小熱膨脹係數之低熱膨脹鑄造合金及其製造方法。 Accordingly, it is an object of the present invention to provide a low thermal expansion casting alloy having a grade C which is generally soluble in the atmosphere and atmospheric casting, and which has a very small thermal expansion coefficient equivalent to that of the super-constant steel, and a method for producing the same.
又，本發明之另一目的係提供一種一方面含有一般可大氣溶解等級之C，一方面具有與超恆範鋼同等之極小熱膨脹係數，且具有比超恆範鋼更優異被切削性之 低熱膨脹鑄造合金及其製造方法。 Further, another object of the present invention is to provide a C which has a general atmospheric dissolution level on the one hand, a very small thermal expansion coefficient equivalent to that of a super-constant steel on the one hand, and a superior machinability than a super-constant steel. Low thermal expansion casting alloy and its manufacturing method.
亦即，本發明提供以下之(1)~(7)。 That is, the present invention provides the following (1) to (7).
(1)一種低熱膨脹鑄造合金，其特徵係以質量%計含有C：超過0.02%、0.15%以下、Si：0.3%以下、Mn：0.25~0.6%、Ni：29~32.5%、Co：5~9.5%，且C含量(質量%)表示為[C]、Co含量(質量%)表示為[Co]時，該等滿足(a)[Co]≧40×[C]+3、(b)[C]≦0.15、(c)[Co]≦(70/3)×[C]+6、(d)[C]>0.02、(e)[Co]≧-20×[C]+6之範圍，Ni含量(質量%)表示為[Ni]，Co含量(質量%)表示為[Co]時，能表示成[Ni]+0.8×[Co]之Ni等量為35.5~36.5%之範圍，其餘部分由Fe及不可避免之雜質所成。 (1) A low thermal expansion casting alloy characterized by containing C: more than 0.02%, 0.15% or less, Si: 0.3% or less, Mn: 0.25 to 0.6%, Ni: 29 to 32.5%, Co: 5 by mass% ~9.5%, and the C content (% by mass) is expressed as [C], and the Co content (% by mass) is expressed as [Co], which satisfies (a) [Co] ≧ 40 × [C] + 3, (b) )[C]≦0.15, (c)[Co]≦(70/3)×[C]+6, (d)[C]>0.02, (e)[Co]≧-20×[C]+6 In the range, the Ni content (% by mass) is expressed as [Ni], and the Co content (% by mass) is expressed as [Co], and the Ni equivalent amount of [Ni] + 0.8 × [Co] can be expressed as 35.5 to 36.5%. The range, the rest is made of Fe and unavoidable impurities.
(2)一種低熱膨脹鑄造合金，其特徵為以質量%計含有C：超過0.02%、0.15%以下、Si：0.3%以下、Mn：0.25~0.6%、S：0.015~0.035%、Ni：29~32.5%、Co：5~9.5%， 且C含量(質量%)表示為[C]、Co含量(質量%)表示為[Co]時，該等滿足(a)[Co]≧40×[C]+3、(b)[C]≦0.15、(c)[Co]≦(70/3)×[C]+6、(d)[C]>0.02、(e)[Co]≧-20×[C]+6之範圍，且Ni含量(質量%)表示為[Ni]，Co含量(質量%)表示為[Co]時，能表示成[Ni]+0.8×[Co]之Ni等量為35.5~36.5%之範圍，進而，Mn含量(質量%)表示為[Mn]，S含量(質量%)表示為[S]，鑄造品之最大厚度(mm)表示為t時，滿足[Mn]/[S]≧46-1335/t+13430/t2，且其餘部分由Fe及不可避免之雜質所成。 (2) A low thermal expansion casting alloy characterized by containing C: more than 0.02%, 0.15% or less, Si: 0.3% or less, Mn: 0.25 to 0.6%, S: 0.015 to 0.035%, and Ni: 29 by mass%. ~32.5%, Co: 5 to 9.5%, and the C content (% by mass) is expressed as [C], and the Co content (% by mass) is expressed as [Co], which satisfies (a) [Co] ≧ 40 × [ C]+3, (b)[C]≦0.15, (c)[Co]≦(70/3)×[C]+6, (d)[C]>0.02, (e)[Co]≧- 20 × [C] + 6 range, and Ni content (% by mass) is expressed as [Ni], and when Co content (% by mass) is expressed as [Co], Ni can be expressed as [Ni] + 0.8 × [Co] The equivalent amount is in the range of 35.5 to 36.5%, and further, the Mn content (% by mass) is expressed as [Mn], the S content (% by mass) is expressed as [S], and the maximum thickness (mm) of the cast product is expressed as t, which is satisfied. [Mn] / [S] ≧ 46-1335 / t + 13430 / t 2 , and the rest is formed by Fe and unavoidable impurities.
(3)一種低熱膨脹鑄造合金，其特徵係具有如上述(1)或(2)之組成，且20~25℃之平均熱膨脹係數為1×10-6/℃以下。 (3) A low thermal expansion casting alloy characterized by having the composition of (1) or (2) above, and an average thermal expansion coefficient of 20 to 25 ° C of 1 × 10 -6 / ° C or less.
(4)一種低熱膨脹鑄造合金，其特徵係具有如上述(1)或(2)之組成，且20~25℃之平均熱膨脹係數為0.5×10-6/℃以下。 (4) A low thermal expansion casting alloy characterized by having the composition of (1) or (2) above, and an average thermal expansion coefficient of from 20 to 25 ° C of 0.5 × 10 -6 / ° C or less.
(5)一種低熱膨脹鑄造合金之製造方法，其特徵係在700~950℃之溫度範圍使具有如上述(1)或(2)之組成之合金加熱後，以5℃/sec.以上之冷卻速度冷卻至450℃以下。 (5) A method for producing a low thermal expansion casting alloy, characterized in that after heating an alloy having the composition of the above (1) or (2) at a temperature ranging from 700 to 950 ° C, cooling is performed at 5 ° C/sec or more The speed is cooled to below 450 °C.
(6)一種低熱膨脹鑄造合金，其特徵係藉由如上述(5)之製造方法獲得之低熱膨脹鑄造合金，且20~25℃之平均熱膨脹係數為1×10-6/℃以下。 (6) A low thermal expansion casting alloy characterized by a low thermal expansion casting alloy obtained by the production method of the above (5), and having an average thermal expansion coefficient of 1 × 10 -6 / ° C or less at 20 to 25 ° C.
(7)一種低熱膨脹鑄造合金，其特徵係藉由如上述(5)之製造方法獲得之低熱膨脹鑄造合金，且20~25℃之平均熱膨脹係數為0.5×10-6/℃以下。 (7) A low thermal expansion casting alloy characterized by a low thermal expansion casting alloy obtained by the production method of the above (5), and having an average thermal expansion coefficient of from 0.5 to 10 -6 / ° C at 20 to 25 ° C.
依據本發明，係提供一種一方面含有通常可大氣溶解及大氣鑄造等級之C，一方面具有與超恆範鋼同等之極小熱膨脹係數之低熱膨脹鑄造合金及其製造方法。 According to the present invention, there is provided a low thermal expansion casting alloy which comprises, on the one hand, a C which is generally soluble in the atmosphere and an atmospheric casting grade, and which has a very small thermal expansion coefficient equivalent to that of the super-constant steel, and a method for producing the same.
此外，依據本發明，提供一種一方面含有一般可大氣溶解等級之C，一方面具有與超恆範鋼同等之極小熱膨脹係數，且具有比超恆範鋼更優異被切削性之低熱膨脹鑄造合金及其製造方法。 Further, according to the present invention, there is provided a low thermal expansion casting alloy which has a general atmospheric solubility level C on the one hand, a very small thermal expansion coefficient equivalent to that of a super-constant steel on the one hand, and a superior machinability than a super-constant steel on the one hand. And its manufacturing method.
圖1係顯示本發明之合金及先前技術之合金中之C含量與Co含量之範圍的圖。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing the range of C content and Co content in the alloy of the present invention and the prior art alloy.
圖2係顯示C含量對本發明之合金與先前超恆範鋼之熱膨脹係數造成之影響的圖。 Figure 2 is a graph showing the effect of C content on the thermal expansion coefficient of the alloy of the present invention and the previous super-constant steel.
圖3係顯示凝固破裂性評價試驗片之圖。 Fig. 3 is a view showing a test piece for evaluation of solidification cracking.
圖4係顯示造成凝固破裂之鑄造品之最大厚度與Mn/S之關係的圖。 Fig. 4 is a graph showing the relationship between the maximum thickness of the cast product causing solidification cracking and Mn/S.
本發明人等為解決上述課題而重複檢討之結果，發現即使將合金中之C含量設為可大氣溶解及大氣鑄 造之等級，但藉由下述i)及ii)仍可獲得與超恆範鋼同等之極小熱膨脹係數：i)依據C含量調整Co含量，ii)依據Co含量而規定Ni含量。 As a result of repeating the review to solve the above problems, the present inventors have found that even if the C content in the alloy is set to be atmospherically soluble and atmospherically cast, The grade is made, but the minimum thermal expansion coefficient equivalent to that of the super-constant steel can be obtained by i) and ii): i) adjusting the Co content according to the C content, and ii) specifying the Ni content according to the Co content.
先前，並未針對C、Ni、Co對熱膨脹係數造成之影響詳細檢討。例如，專利文獻1中雖記載C、Ni及Co之範圍之限定理由，但實施例之組成僅為C係0.01%左右之超恆範鋼組成(32%Ni-5%Co-Fe)，藉此獲得1×10-6/℃以下之熱膨脹係數，但並未教示申請專利範圍之組成能獲得1×10-6/℃以下之熱膨脹係數。 Previously, there was no detailed review of the effects of C, Ni, and Co on the coefficient of thermal expansion. For example, in Patent Document 1, the reason for limiting the range of C, Ni, and Co is described, but the composition of the embodiment is only a composition of super constant steel of about 0.01% of C system (32% Ni-5% Co-Fe). This achieves a thermal expansion coefficient of 1 × 10 -6 /° C or less, but does not teach that the composition of the patent application can obtain a thermal expansion coefficient of 1 × 10 -6 /° C. or less.
總括先前之見解時，將超恆範鋼之C含量與Co含量之範圍設為以圖1之區域A所示之範圍。亦即，先前認為若將C抑制為雜質程度，則在4~6%Co之範圍可確實成為1×10-6/℃以下之熱膨脹係數，但C增加時其範圍變狹窄，C超過0.05%時即使調整Co量仍無法獲得1×10-6/℃以下之熱膨脹係數。 In the case of the previous findings, the range of the C content and the Co content of the super-constant steel is set to the range shown by the area A of FIG. In other words, it has been previously considered that if C is suppressed to an impurity level, the thermal expansion coefficient of 1×10 -6 /° C. or less can be surely obtained in the range of 4 to 6% Co, but the range becomes narrow when C increases, and C exceeds 0.05%. Even if the Co amount is adjusted, the thermal expansion coefficient of 1 × 10 -6 /° C or less cannot be obtained.
先前之超恆範鋼組成(圖1之區域A)中，於可獲得大氣溶解之鑄造品之C為超過0.02%~0.05%以下之範圍(圖1之區域B)，雖可獲得1×10-6/℃以下之熱膨脹係數，但在大氣溶解下製造鑄造品時，由於除了C以外，基於脫氧或改善鑄造性的目的而添加能增加熱膨脹係數之Si或Mn，故實際上產生熱膨脹係數超過1×10-6/℃之區域。因此，欲獲得1×10-6/℃以下之熱膨脹係數時，如專利文獻1所見，有必要將C限制為更低。其結果，在鑄造材料 中，圖1之區域B成為平行移動至低C側之形態，若未進行成分調整至極限之範圍，則認為難以確實製造適當之鑄造品。 In the composition of the previous super-constant steel (region A in Fig. 1), the C of the casting which can be dissolved in the atmosphere is in the range of more than 0.02% to 0.05% (region B in Fig. 1), although 1×10 is obtained. a thermal expansion coefficient of -6 /°C or less, but when a cast product is produced under atmospheric dissolution, since Si or Mn which increases the thermal expansion coefficient is added for the purpose of deoxidation or improvement of castability other than C, the thermal expansion coefficient actually exceeds 1 × 10 -6 / °C area. Therefore, when a thermal expansion coefficient of 1 × 10 -6 /° C or less is to be obtained, as seen in Patent Document 1, it is necessary to limit C to be lower. As a result, in the cast material, the region B in Fig. 1 is moved in parallel to the low C side, and if the component is not adjusted to the limit, it is considered that it is difficult to reliably manufacture a suitable cast product.
相對於此，本發明係以使C含量在可大氣溶解‧大氣鑄造之超過0.02%之範圍為前提，檢討獲得1×10-6/℃以下之熱膨脹係數之組成的結果，新發現藉由使C含量與Co含量之範圍滿足圖1之區域C之範圍，同時依據Co含量而規定Ni含量，能獲得1×10-6/℃以下之熱膨脹係數。 On the other hand, in the present invention, the result of obtaining a composition of a thermal expansion coefficient of 1 × 10 -6 /° C or less is evaluated on the premise that the C content is in the range of more than 0.02% of atmospheric melting and atmospheric casting, and the new findings are The range of the C content and the Co content satisfies the range of the region C of Fig. 1, and the Ni content is defined in accordance with the Co content, and a thermal expansion coefficient of 1 × 10 -6 /° C or less can be obtained.
此外，發現藉由如上述般規定C含量、Co含量、及Ni含量，進而將S含量、Mn含量及該等之比規定在特定範圍，可使硫化物適當分佈在合金組織中而可促進工具潤滑，獲得具有1×10-6/℃以下之低膨脹率且不產生凝固破裂之良好被切削性之鑄造合金。 In addition, it has been found that by specifying the C content, the Co content, and the Ni content as described above, and further adjusting the S content, the Mn content, and the ratios to a specific range, the sulfide can be appropriately distributed in the alloy structure to promote the tool. Lubrication, a cast alloy having a good machinability with a low expansion ratio of 1 × 10 -6 / ° C or less and no solidification cracking is obtained.
而且，亦發現為使上述組成之合金成為1×10-6/℃以下之低膨脹率，適當控制熱處理亦有效。 Further, it has been found that it is effective to appropriately control the heat treatment so that the alloy having the above composition has a low expansion ratio of 1 × 10 -6 /°C or less.
本發明係基於以上見解而完成者。 The present invention has been completed based on the above findings.
以下，參照附屬圖式對本發明之實施形態加以說明。 Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
第1實施形態係一方面含有通常可大氣溶解及大氣鑄造之等級的C，一方面獲得與超恆範鋼同等之低熱膨脹係數之鑄造合金者。 The first embodiment is a one which contains C which is generally soluble in the atmosphere and cast in the atmosphere, and which has a low thermal expansion coefficient equivalent to that of the super-constant steel.
以下，針對本實施形態中之限制理由加以詳細說明。又，只要沒有特別指明則成分中之%表示為質量%，熱膨脹係數為20~25℃之平均熱膨脹係數。 Hereinafter, the reasons for limitation in the present embodiment will be described in detail. Further, unless otherwise specified, % of the components are expressed by mass%, and the coefficient of thermal expansion is an average thermal expansion coefficient of 20 to 25 °C.
‧C：超過0.02%、0.15%以下 ‧C: more than 0.02%, less than 0.15%
C係使熱膨脹係數顯著增加之元素，先前之超恆範鋼組成(32%Ni-5%Co-其餘為Fe)中，含有超過0.02%之C時，難以獲得1×10-6/℃以下之低熱膨脹係數。然而，C具有改善超恆範鋼組成之低熱膨脹合金鑄造品之鑄造性或健全性之效果，本發明係以即使於大氣溶解中仍可獲得健全之鑄造品之方式進行適當之鑄造設計，將C含量設為超過0.02%。具體而言，如圖1所示(詳述於後)，依據C量調整Co量，藉此即使C含量超過0.02%仍可獲得1×10-6/℃以下之低熱膨脹係數。然而，其含量超過0.15%時，組織中之一部分中析出石墨，使固溶C之量產生變化，故即使調整Co量仍無法獲得1×10-6/℃以下之熱膨脹係數。因此，將C含量設為超過0.02%，且0.15%以下之範圍。 The C system is an element which significantly increases the coefficient of thermal expansion. When the composition of the previous super-constant steel (32% Ni-5% Co-the balance is Fe) contains more than 0.02% of C, it is difficult to obtain 1×10 -6 /°C or less. Low coefficient of thermal expansion. However, C has the effect of improving the castability or soundness of the low thermal expansion alloy casting of the composition of the super-constant steel, and the present invention performs the appropriate casting design in such a manner that a sound casting can be obtained even in the atmosphere. The C content was set to exceed 0.02%. Specifically, as shown in FIG. 1 (detailed later), the amount of Co is adjusted in accordance with the amount of C, whereby a low thermal expansion coefficient of 1 × 10 -6 /° C. or less can be obtained even if the C content exceeds 0.02%. However, when the content exceeds 0.15%, graphite is precipitated in one part of the structure, and the amount of solid solution C is changed. Therefore, even if the amount of Co is adjusted, a thermal expansion coefficient of 1 × 10 -6 /° C or less cannot be obtained. Therefore, the C content is set to be more than 0.02% and not more than 0.15%.
圖2顯示先前合金(超恆範鋼)及本發明之合金中之C含量與熱膨脹率之關係。如該圖所示，可知本發明中即使C含量較多仍可獲得低熱膨脹。 Figure 2 shows the relationship between the C content of the prior alloy (Super Constant Steel) and the alloy of the present invention and the coefficient of thermal expansion. As shown in the figure, it is understood that in the present invention, even if the C content is large, low thermal expansion can be obtained.
‧Si：0.3%以下 ‧Si: less than 0.3%
Si係以脫氧及改善熱液流動性為目的而添加之元素。 然而，其含量超過0.3%時，與C同樣無法忽略熱膨脹係數之增加。因此，將Si含量設為0.3%以下。 Si is an element added for the purpose of deoxidation and improvement of hydrothermal fluidity. However, when the content exceeds 0.3%, the increase in the coefficient of thermal expansion cannot be ignored as with C. Therefore, the Si content is set to 0.3% or less.
‧Mn：0.25~0.6% ‧Mn: 0.25~0.6%
Mn係對脫氧有效之元素。然而，其含量未達0.25%時其效果較少，超過0.6%時熱膨脹係數之增加變大。因此，將Mn含量設為0.25~0.6%之範圍。 Mn is an element effective for deoxidation. However, when the content is less than 0.25%, the effect is small, and when it exceeds 0.6%, the increase in the coefficient of thermal expansion becomes large. Therefore, the Mn content is set in the range of 0.25 to 0.6%.
‧Co：5~9.5% ‧Co: 5~9.5%
Co係與後述之Ni一起決定熱膨脹係數之重要元素，而且係為了用於獲得比單獨添加Ni時更小之熱膨脹係數而不可或缺之元素。 The Co system determines an important element of the thermal expansion coefficient together with Ni described later, and is an element which is indispensable for obtaining a thermal expansion coefficient smaller than that when Ni is separately added.
未達5%時熱膨脹係數超過1×10-6/℃，超過9.5%時即使調整後述相對於C量之Co量熱膨脹係數仍超過1×10-6/℃。因此，將Co含量設為5~9.5%之範圍。 When the temperature is less than 5%, the coefficient of thermal expansion exceeds 1 × 10 -6 / ° C. When the amount exceeds 9.5%, the coefficient of thermal expansion of Co relative to the amount of C described later exceeds 1 × 10 -6 / ° C. Therefore, the Co content is set to be in the range of 5 to 9.5%.
‧Ni：29~32.5% ‧Ni: 29~32.5%
Ni係與Co一起決定熱膨脹係數之重要元素，藉由依據Co量而調整成後述範圍可使熱膨脹係數成為1×10-6/℃以下。然而，Ni未達29%，或超過32.5%時，即使藉前述之調整，熱膨脹係數仍超過1×10-6/℃。因此，將Ni設為29~32.5%之範圍。 The Ni system and the Co determine an important element of the coefficient of thermal expansion, and the thermal expansion coefficient can be set to 1 × 10 -6 /° C or less by adjusting the amount of Co to the range described later. However, when Ni is less than 29%, or exceeds 32.5%, the thermal expansion coefficient exceeds 1 × 10 -6 / ° C even with the aforementioned adjustment. Therefore, Ni is set in the range of 29 to 32.5%.
‧Co及C係滿足下述之範圍 ‧Co and C systems meet the following range
(a)[Co]≧40×[C]+3、(b)[C]≦0.15、(c)[Co]≦(70/3)×[C]+6、(d)[C]>0.02、(e)[Co]≧-20×[C]+6。 (a) [Co]≧40×[C]+3, (b)[C]≦0.15, (c)[Co]≦(70/3)×[C]+6, (d)[C]> 0.02, (e) [Co] ≧-20 × [C] + 6.
‧[Ni]+0.8×[Co]為35.5~36.5%之範圍。 ‧[Ni]+0.8×[Co] is in the range of 35.5~36.5%.
本發明人等詳細檢討合金中之C含量與Co含量之結果，新發現先前從未檢討之若滿足圖1之區域C所示之(a)[Co]≧40×[C]+3、(b)[C]≦0.15、(c)[Co]≦(70/3)×[C]+6、(d)[C]>0.02、(e)[Co]≧-20×[C]+6之範圍，則能表示成[Ni]+0.8×[Co]之Ni等量為35.5~36.5%之範圍，且獲得1×10-6/℃以下之熱膨脹係數。但，[C]、[Co]、[Ni]為各元素之含量(質量%)。 The present inventors reviewed the results of the C content and the Co content in the alloy in detail, and newly discovered (a) [Co] ≧ 40 × [C] + 3, which is not previously reviewed, if it satisfies the area C of Fig. 1 . b) [C] ≦ 0.15, (c) [Co] ≦ (70/3) × [C] + 6, (d) [C] > 0.02, (e) [Co] ≧ -20 × [C] + In the range of 6, it can be expressed as a range of 35.5 to 36.5% of Ni equivalent of [Ni] + 0.8 × [Co], and a thermal expansion coefficient of 1 × 10 -6 / ° C or less is obtained. However, [C], [Co], and [Ni] are the contents (% by mass) of each element.
偏離圖1之區域C時，產生如下缺陷。亦即，[Co]<40×[C]+3(區域C之下側)時熱膨脹係數超過1×10-6/℃，[Co]<-20×[C]+6之區域(區域C之下側)時在鑄造合金中難以確實獲得1×10-6/℃以下之熱膨脹係數，[Co]>(70/3)×[C]+6之區域(區域C之上側)時，組織之一部分因麻田散鐵體變態(Martensitic transformation)而引起膨脹，在[C]>0.15之區域(區域C之右側)時，C超過固溶極限，固溶成過飽和，成為石墨而析出，使熱膨脹係數變得不安定，[C]≦0.02之區域(區域C之左側)時鑄造品多發生缺陷。 When deviating from the area C of Fig. 1, the following defects occur. That is, when [Co]<40×[C]+3 (the lower side of the region C), the coefficient of thermal expansion exceeds 1×10 -6 /°C, and the region of [Co]<-20×[C]+6 (region C In the case of the lower side, it is difficult to obtain a thermal expansion coefficient of 1 × 10 -6 /° C or less in the cast alloy, and a region of [Co]>(70/3)×[C]+6 (the upper side of the region C), the structure Part of it is caused by Martensitic transformation. In the region of [C]>0.15 (on the right side of the region C), C exceeds the solid solution limit, solid solution becomes supersaturated, and it becomes graphite and precipitates, causing thermal expansion. The coefficient becomes unstable, and the casting product is often defective when [C] ≦ 0.02 (the left side of the area C).
此外，Fe-Ni-Co合金之低熱膨脹性在表示成 [Ni]+0.8×[Co]之Ni等量為35.5~36.5%之範圍內能顯著獲得，未達35.5%，或超過36.6%均難以獲得期望之低熱膨脹性。因此，將Ni等量設為35.5~36.5%之範圍。 In addition, the low thermal expansion of Fe-Ni-Co alloy is expressed in The Ni equivalent amount of [Ni]+0.8×[Co] can be remarkably obtained in the range of 35.5 to 36.5%, and it is difficult to obtain the desired low thermal expansion property when it is less than 35.5% or more than 36.6%. Therefore, the Ni equivalent is set to a range of 35.5 to 36.5%.
其餘部分為Fe及不可避免之雜質。本實施形態中S係以雜質含有。 The rest is Fe and unavoidable impurities. In the present embodiment, S is contained as an impurity.
使該等組成範圍之合金在高溫加熱後急冷時，可減小熱膨脹係數。其理由認為係急冷時產生之內應力之作用使磁化狀態產生變化，對自發磁化應變造成影響之故。加熱溫度未達700℃時，低熱膨脹效果不充分，且，超過950℃時效果並未提高，反而有產生變形或破裂之危險。加熱後，達450℃之平均冷卻速度未達5℃/sec時，內應力發生較小，熱膨脹係數之減低效果少。因此，在700~950℃之溫度範圍加熱後，以5℃/sec以上之冷卻速度冷卻至450℃以下。 When the alloys of the above composition range are quenched after heating at a high temperature, the coefficient of thermal expansion can be reduced. The reason for this is considered to be that the action of the internal stress generated during quenching causes a change in the magnetization state and affects the spontaneous magnetization strain. When the heating temperature is less than 700 ° C, the effect of low thermal expansion is insufficient, and when the temperature exceeds 950 ° C, the effect is not improved, and there is a risk of deformation or cracking. After heating, when the average cooling rate of 450 ° C is less than 5 ° C / sec, the internal stress is small, and the effect of reducing the thermal expansion coefficient is small. Therefore, after heating in a temperature range of 700 to 950 ° C, it is cooled to 450 ° C or lower at a cooling rate of 5 ° C / sec or more.
如以上之本實施形態之鑄造合金可獲得1×10-6/℃以下之低熱膨脹率，進而藉由使組成適度化，可獲得0.5×10-6/℃以下之極低熱膨脹率。 As described above, the casting alloy of the present embodiment can obtain a low thermal expansion coefficient of 1 × 10 -6 /° C. or less, and further, by appropriately setting the composition, an extremely low thermal expansion coefficient of 0.5 × 10 -6 /° C. or lower can be obtained.
第1實施形態中由於一方面具有與超恆範鋼同等之低熱膨脹係數，一方面含有一般可大氣溶解及大氣鑄造等級之C，故可獲得低熱膨脹鑄造合金。因此，可不熔接而獲得低熱膨脹之複雜形狀品或大型零件。 In the first embodiment, since it has a low thermal expansion coefficient equivalent to that of the super-constant steel, and on the other hand, it contains C which is generally soluble in the atmosphere and atmospheric casting grade, so that a low thermal expansion casting alloy can be obtained. Therefore, it is possible to obtain a complicated shape product or a large-sized part with low thermal expansion without welding.
第2實施形態係一方面含有一般可大氣溶解及大氣鑄造等級之C，一方面獲得與超恆範鋼同等之熱膨脹係數，進而被切削性亦優異者。 In the second embodiment, on the one hand, C which is generally soluble in the atmosphere and cast in the atmosphere is contained, and on the other hand, the thermal expansion coefficient equivalent to that of the super-constant steel is obtained, and the machinability is also excellent.
以下，針對本實施形態中之限制理由加以詳細說明。 Hereinafter, the reasons for limitation in the present embodiment will be described in detail.
本實施形態中，C、Si、Co、Ni之含量、及C含量與Co含量之關係、Ni當量之範圍、及製造條件係與第1實施形態相同。以下，針對第2實施形態特有之條件加以說明。 In the present embodiment, the content of C, Si, Co, and Ni, the relationship between the C content and the Co content, the range of the Ni equivalent, and the production conditions are the same as those in the first embodiment. Hereinafter, conditions specific to the second embodiment will be described.
‧Mn：0.25~0.6% ‧Mn: 0.25~0.6%
Mn係對脫氧有效之元素，且扮演如後述般與S形成硫化物而提高被切削性之重要角色。其含量未達0.25%時其效果較少，超過0.6%時熱膨脹係數之增加變大。因此，將Mn含量設為0.25~0.6%之範圍。 Mn is an element effective for deoxidation, and plays an important role in forming a sulfide with S to improve machinability as will be described later. When the content is less than 0.25%, the effect is less, and when it exceeds 0.6%, the increase of the thermal expansion coefficient becomes large. Therefore, the Mn content is set in the range of 0.25 to 0.6%.
‧S：0.015~0.035% ‧S: 0.015~0.035%
S由於與Mn形成硫化物，而有助於提高被切削性，故在本實施形態中係積極添加。然而，合金中含較多量時，於結晶粒界生成低熔點之FeS而脆化，成為延展性降低或破裂之原因，超過0.035%時容易於複雜形狀或大型鑄造品中產生凝固破裂。另一方面，其含量未達0.015%時提高被切削性之效果小。因此，將S含量設為 0.015~0.035%之範圍。 Since S forms a sulfide with Mn and contributes to improvement of machinability, it is actively added in the present embodiment. However, when a large amount is contained in the alloy, FeS having a low melting point is formed at the grain boundary to embrittle, which causes a decrease in ductility or cracking. When it exceeds 0.035%, it is easy to cause solidification cracking in a complicated shape or a large cast product. On the other hand, when the content is less than 0.015%, the effect of improving the machinability is small. Therefore, set the S content to Range of 0.015~0.035%.
‧[Mn]/[S]≧46-1335/t+13430/t2 ‧[Mn]/[S]≧46-1335/t+13430/t 2
(但，[Mn]、[S]表示該等之含量，t表示鑄造品之最大厚度(mm)) (However, [Mn], [S] represent the content of these, and t represents the maximum thickness (mm) of the cast product)
[Mn]/[S]係左右硫化物之生成量或組成，決定凝固破裂傾向之重要參數。且凝固破裂傾向不僅受Mn與S之比影響，亦受t影響。前述之Mn及S之範圍中，[Mn]/[S]未達46-1335/t+13430/t2時，Mn相對於S為不足，過量之S形成上述之FeS，成為凝固破裂等之原因。另一方面，[Mn]/[S]為46-1335/t+13430/t2以上時，S以高熔點之MnS存在，故不易引起凝固破裂。 The amount or composition of the [Mn]/[S]-based sulfide is an important parameter that determines the tendency of solidification and fracture. Moreover, the tendency of solidification and rupture is affected not only by the ratio of Mn to S but also by t. In the range of Mn and S described above, when [Mn]/[S] is less than 46-1335/t+13430/t 2 , Mn is insufficient with respect to S, and an excessive amount of S forms the above-described FeS, which causes solidification cracking or the like. the reason. On the other hand, when [Mn]/[S] is 46-1335/t+13430/t 2 or more, S exists as a high melting point MnS, so that it is less likely to cause solidification cracking.
由於鑄造品之最大厚度t(mm)對於凝固破裂之影響由於與圖3所示之凝固破裂試驗片之R(mm)有關，故可使用破裂試驗片掌握t與凝固破裂之關係。依據本發明人之見解，R與t之關係以t=500/R表示。亦即，R愈小愈可模擬厚壁之鑄造品。 Since the influence of the maximum thickness t (mm) of the cast product on the solidification crack is related to R (mm) of the solidification fracture test piece shown in Fig. 3, the relationship between t and solidification crack can be grasped using the fracture test piece. According to the inventors' knowledge, the relationship between R and t is represented by t = 500 / R. That is, the smaller the R, the more it can simulate thick-walled castings.
實際上圖3所示之凝固破裂試驗片之R之大小與因[Mn]/[S]所致之凝固破裂有無係使用表2所示之實施例之No.21~24掌握，結果示於圖4。圖4同時顯示R之大小以及相當之最大厚度t(mm)。 Actually, the size of R of the solidification fracture test piece shown in Fig. 3 and the presence or absence of solidification fracture due to [Mn]/[S] were grasped using No. 21 to 24 of the examples shown in Table 2, and the results are shown in Figure 4. Figure 4 also shows the size of R and the equivalent maximum thickness t (mm).
如圖4所示，R愈小，亦即相當厚度愈大，則難以產生凝固破裂之[Mn]/[S]之值愈大，難以發生凝固破裂之邊界線以46-1335/t+13430/t2表示。因此，規定為 [Mn]/[S]≧46-1335/t+13430/t2。例如，對於最大厚度為100mm之鑄造品，若將Mn/S設為大約34左右則可有效地防止凝固破裂。 As shown in Fig. 4, the smaller the R, that is, the larger the thickness, the larger the value of [Mn]/[S] which is hard to cause solidification cracking, and the boundary line where solidification cracking is difficult to occur is 46-1335/t+13430 /t 2 means. Therefore, it is specified as [Mn] / [S] ≧ 46-1335 / t + 13430 / t 2 . For example, for a cast product having a maximum thickness of 100 mm, if Mn/S is set to about 34 or so, solidification cracking can be effectively prevented.
本實施形態中，C、Si、Mn、S、Co、Ni之其餘部分為Fe及不可避免之雜質。 In the present embodiment, the remaining portions of C, Si, Mn, S, Co, and Ni are Fe and unavoidable impurities.
又，本實施形態為第1實施形態之合金中進一步含有S之組成，只要為本實施形態之範圍之S含量，則對熱膨脹不會造成影響。亦即，本實施形態之鑄造合金亦與第1實施形態之鑄造合金同樣，可獲得1×10-6/℃以下之低熱膨脹率，進而藉由使組成適度化，可獲得0.5×10-6/℃以下之極低熱膨脹率。 Further, in the present embodiment, the alloy of the first embodiment further contains the composition of S, and the S content in the range of the present embodiment does not affect the thermal expansion. In other words, the cast alloy of the present embodiment can obtain a low coefficient of thermal expansion of 1 × 10 -6 /° C. or less, and a composition of 0.5 × 10 -6 can be obtained by appropriately setting the composition as in the cast alloy of the first embodiment. Very low thermal expansion rate below /°C.
第2實施形態一方面具有與超恆範鋼同等之低熱膨脹係數，一方面含有一般可大氣溶解及大氣鑄造等級之C，且不會產生凝固破裂而提高被切削性，可獲得快削性低熱膨脹鑄造合金。因此，可不熔接且以良好切削性製作低熱膨脹之複雜形狀品或大型零件。 In the second embodiment, on the one hand, it has a low thermal expansion coefficient equivalent to that of the super-constant steel, and on the other hand, it contains a C which is generally soluble in the atmosphere and cast in the atmosphere, and does not cause solidification cracking to improve the machinability, and low cutting property can be obtained. Thermal expansion casting alloy. Therefore, it is possible to produce a complicated shape product or a large-sized part with low thermal expansion without welding and with good machinability.
以下，針對本發明之實施例加以說明。 Hereinafter, embodiments of the invention will be described.
第1實施例係對應於第1實施形態者。 The first embodiment corresponds to the first embodiment.
此處，以高頻感應爐使表1所示之各化學組成之合金大氣溶解，依據JIS G0307之圖1 b)為準鑄造供試材。所 有鑄模均使用CO2法矽砂模。 Here, the alloy of each chemical composition shown in Table 1 was dissolved in the atmosphere by a high-frequency induction furnace, and the test material was cast in accordance with Fig. 1 b) of JIS G0307. All molds were sand molds using a CO 2 method.
對各供試材施以表3之條件8之熱處理後，採取 6×12mm之熱膨脹試驗片，以雷射干涉式熱膨脹計測定20~25℃間之平均熱膨脹係數。 After each of the test materials was subjected to the heat treatment of Condition 8 of Table 3, A 6×12 mm thermal expansion test piece was measured by a laser interferometric thermal expansion meter to measure an average thermal expansion coefficient between 20 and 25 °C.
其結果示於表1。如表1所示，本發明合金的No.1~7在20~25℃間之平均熱膨脹係數均為1×10-6/℃以下，其中No.1與No.2及No.7為0.5×10-6/℃以下，尤其No.1未達0.2×10-6/℃，與先前之超恆範鋼同等，確認具有對應於最近嚴格要求之特性。且，該等完全無鑄造缺陷，獲得良好之鑄造性。 The results are shown in Table 1. As shown in Table 1, the average thermal expansion coefficients of Nos. 1 to 7 of the alloy of the present invention at 20 to 25 ° C were all 1 × 10 -6 / ° C or less, wherein No. 1 and No. 2 and No. 7 were 0.5. ×10 -6 /°C or less, especially No.1 is less than 0.2×10 -6 /°C, which is equivalent to the previous super-constant steel, and has characteristics corresponding to the most recent strict requirements. Moreover, these are completely free of casting defects and achieve good castability.
另一方面，比較例中，No.8之C由於未達下限，故發生氣體缺陷，鑄造性差。又，關於No.9~15，No.9之Si與Ni超過上限，Co未達下限，No.10之Ni未達下限，Co超過上限，進而C含量與Co含量之關係偏離圖1之發明範圍，產生麻田散鐵體變態，No.11及No.12之各元素雖在範圍內，但C含量與Co含量之關係偏離圖1之發明範圍，產生麻田散鐵體變態，No.13及No.14均係各元素均在範圍內，但Ni等量於No.13未達下限，No.14則超過上限，進而No.15之C超過上限而在組織中產生石墨，使組織變得不安定，均無法獲得期望之熱膨脹係數。 On the other hand, in the comparative example, since the C of No. 8 did not reach the lower limit, gas defects occurred and the castability was inferior. Further, regarding No. 9 to 15, No. 9 and Si have exceeded the upper limit, Co has not reached the lower limit, No. 10 has not reached the lower limit of Ni, Co exceeds the upper limit, and further, the relationship between the C content and the Co content deviates from the invention of FIG. The range is such that the elements of No.11 and No.12 are in the range, but the relationship between the C content and the Co content deviates from the scope of the invention of Fig. 1, resulting in the metamorphosis of the Ma Tian loose body, No. 13 and No. 14 is in the range of each element, but Ni is equal to No. 13 and does not reach the lower limit, No. 14 exceeds the upper limit, and No. 15 C exceeds the upper limit to generate graphite in the structure, and the structure becomes Unstable, the desired coefficient of thermal expansion cannot be obtained.
第2實施例係對應於第2實施形態者。 The second embodiment corresponds to the second embodiment.
此處，以高頻感應爐使表2所示之各化學組成之合金大氣溶解，依據JIS G0307之圖1 b)為準鑄造供試材及60mm×250mm×25mm之被切削性試驗片，且關於表2之No.21~No.24及No.37之合金，係鑄造圖3所示之凝固破裂試驗片。所有鑄模均使用CO2法矽砂模。 Here, the alloy of each chemical composition shown in Table 2 is dissolved in the atmosphere by a high-frequency induction furnace, and the test piece and the machinability test piece of 60 mm × 250 mm × 25 mm are cast in accordance with JIS G0307, Fig. 1 b). Regarding the alloys of No. 21 to No. 24 and No. 37 in Table 2, the solidification fracture test piece shown in Fig. 3 was cast. All molds were sand molds using a CO 2 method.
與第1實施例同樣施以熱處理後，自供試材採取 6×12mm之熱膨脹試驗片，以雷射干涉式熱膨脹計測定20~25℃間之平均熱膨脹係數。 After the heat treatment is carried out in the same manner as in the first embodiment, the self-test material is taken. A 6×12 mm thermal expansion test piece was measured by a laser interferometric thermal expansion meter to measure an average thermal expansion coefficient between 20 and 25 °C.
破裂試驗片係以染色浸透探傷檢查法確認圖3中之4種之R部有無破裂。 In the rupture test piece, it was confirmed by dye staining flaw detection method whether or not the R portions of the four types in Fig. 3 were broken.
被削性試驗係以使60mm×250mm之2面成為平行之方式經平面研削後，使用安裝有 5mm之高速度鋼製工具之鑽孔機、以轉數1274RPM、推進0.2mm/轉、無潤滑進行深度10mm之孔洞加工，可穿孔25孔以上時判定為被切削性良好。 The machinability test is performed after the plane is ground in such a manner that the two faces of 60 mm × 250 mm are parallel. A 5 mm high-speed steel tool drilling machine is used for hole machining with a rotation speed of 1274 RPM, a push of 0.2 mm/rev, and no lubrication for a depth of 10 mm, and it is judged that the machinability is good when the hole is punched by 25 holes or more.
該等結果示於表2。如表2所示，本發明之合金的No.21~28在20~25℃間之平均熱膨脹係數均為1×10-6/℃以下，其中No.21與No.27及No.28為0.5×10-6/℃以下，尤其No.28為0.2×10-6/℃與過去之超恆範鋼為同等，確認具有對應於最近嚴格要求之特性。且，鑄造時不產生氣體缺陷，且凝固破裂試驗片之所有R部亦 未確認破裂，顯示良好的耐凝固破裂。進而，被切削性亦良好。 These results are shown in Table 2. As shown in Table 2, the average thermal expansion coefficients of No. 21 to 28 of the alloy of the present invention at 20 to 25 ° C were 1 × 10 -6 / ° C or less, of which No. 21 and No. 27 and No. 28 were 0.5 × 10 -6 / ° C or less, especially No. 28 is 0.2 × 10 -6 / ° C is equivalent to the past Super Hengfan steel, and it is confirmed that it has characteristics corresponding to the most recent strict requirements. Further, no gas defects were generated at the time of casting, and all of the R portions of the coagulation fracture test piece were not confirmed to be broken, showing good resistance to solidification cracking. Further, the machinability is also good.
另一方面，比較例中，No.29由於C未達下限，故熱膨脹係數低，發生氣體缺陷，鑄造性差。且，關於No.30~35，No.30係Si超過上限，C含量與Co含量之關係偏離圖1之發明範圍，No.31係各元素在範圍內但C含量與Co含量之關係偏離圖1之發明範圍，No.32係Ni未達下限，C超過上限在組織中產生石墨，組織變不安定，No.33係Ni未達下限而出現麻田散鐵變態，No.34係Ni等量未達下限，No.35係Ni等量超過上限，No.36係Co未達下限，均無法獲得期望之熱膨脹係數。再者，比較例的No.37之Mn/S之值比在R20未產生破裂之15小，故破裂試驗片之所有R部均確認破裂。另外，比較例之No.38係S未達下限故被切削性不良。 On the other hand, in the comparative example, since No. 29 did not reach the lower limit, the coefficient of thermal expansion was low, gas defects occurred, and castability was inferior. Further, regarding No. 30 to 35, the No. 30 system Si exceeds the upper limit, and the relationship between the C content and the Co content deviates from the scope of the invention of Fig. 1, and the relationship between the C content and the Co content in the range of No. 31 is in the range. In the scope of the invention of No. 32, No. 32 is not lower than the lower limit of C, and C exceeds the upper limit to produce graphite in the structure, and the structure becomes unstable. No. 33 is not lower than the lower limit, and the granules are metamorphosed, and No. 34 is Ni. When the lower limit is not reached, the No. 35 series Ni amount exceeds the upper limit, and the No. 36 system Co does not reach the lower limit, and the desired thermal expansion coefficient cannot be obtained. Further, in Comparative Example No. 37, the value of Mn/S was smaller than 15 in which no crack occurred in R20, and therefore all of the R portions of the fracture test piece were confirmed to be broken. Further, in the comparative example No. 38, S did not reach the lower limit, so that the machinability was poor.
第3實施例係與製造條件有關者。 The third embodiment is related to the manufacturing conditions.
此處，首先準備具有表1之No.5之組成，以表3所示之條件1~13之各熱處理條件進行熱處理而準備複數試驗體，求出熱膨脹係數。其結果示於表4。如表4所示，若為滿足在700~950℃之溫度範圍加熱後，以5℃/sec.以上之冷卻速度冷卻至450℃以下之條件之條件5、6、8、9、11，則確認熱膨脹係數為1×10-6/℃以下，亦未發生破裂。相對於此，偏離該條件之條件1、2、3、4、7、10、12之熱膨脹係數超過1×10-6/℃，條件13之熱膨脹係數雖為1×10-6/℃以下，但於試驗體見到微細破裂。 Here, first, the composition having No. 5 of Table 1 was prepared, and heat treatment was performed under the respective heat treatment conditions of Conditions 1 to 13 shown in Table 3 to prepare a plurality of test pieces, and the thermal expansion coefficient was determined. The results are shown in Table 4. As shown in Table 4, if it satisfies the conditions 5, 6, 8, 9, and 11 which are heated to a temperature of 700 ° C to 950 ° C and then cooled to 450 ° C or lower at a cooling rate of 5 ° C / sec or more, It was confirmed that the coefficient of thermal expansion was 1 × 10 -6 / ° C or less, and no crack occurred. On the other hand, the thermal expansion coefficients of the conditions 1, 2, 3, 4, 7, 10, and 12 which deviate from the conditions exceed 1 × 10 -6 / ° C, and the thermal expansion coefficient of the condition 13 is 1 × 10 -6 / ° C or less. However, fine cracking was observed in the test body.
接著，同樣以表3所示之條件1~13之各熱處理條件熱處理表2之No.25之組成合金而準備複數試驗體，求出熱膨脹係數。其結果示於表5。如表5所示，若為與No.5之組成同樣，滿足在700~950℃之溫度範圍加熱後，以5℃/sec.以上之冷卻速度冷卻至450℃以下之條件之條件5、6、8、9、11，則確認熱膨脹係數為1×10-6/℃以下，亦未發生破裂。相對於此，偏離該條件之條件1、2、3、4、7、10、12之熱膨脹係數超過1×10-6/℃，條件13之熱膨脹係數雖為1×10-6/℃以下，但於試驗體見到微細破裂。 Then, the alloy of No. 25 of Table 2 was heat-treated under the respective heat treatment conditions of Conditions 1 to 13 shown in Table 3 to prepare a plurality of test pieces, and the coefficient of thermal expansion was determined. The results are shown in Table 5. As shown in Table 5, in the same manner as the composition of No. 5, the conditions of cooling to a temperature of 700 to 950 ° C and cooling to a temperature of 450 ° C or lower at a cooling rate of 5 ° C / sec. or more are satisfied. 8, 8, and 11, it was confirmed that the coefficient of thermal expansion was 1 × 10 -6 / ° C or less, and no crack occurred. On the other hand, the thermal expansion coefficients of the conditions 1, 2, 3, 4, 7, 10, and 12 which deviate from the conditions exceed 1 × 10 -6 / ° C, and the thermal expansion coefficient of the condition 13 is 1 × 10 -6 / ° C or less. However, fine cracking was observed in the test body.
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