TW201321525A - Ni-based corrosion-resistant wear-resistant alloy - Google Patents
Ni-based corrosion-resistant wear-resistant alloy Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 71
- 239000000956 alloy Substances 0.000 title claims abstract description 71
- 238000005260 corrosion Methods 0.000 title claims abstract description 42
- 230000007797 corrosion Effects 0.000 title claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000000155 melt Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 4
- 239000007858 starting material Substances 0.000 abstract 3
- 238000005507 spraying Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000011195 cermet Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910005569 NiB Inorganic materials 0.000 description 1
- 229910005883 NiSi Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/68—Barrels or cylinders
- B29C48/6803—Materials, coating or lining therefor
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- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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- Extrusion Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
本發明關於Ni基底耐蝕耐磨耗合金。 The invention relates to a Ni base corrosion resistant and wear resistant alloy.
最近，太陽電池模組用保護薄片、水處理過濾器等之氟系樹脂成形品之需求係有逐年增加之傾向。氟系樹脂零件係使用壓出機、射出成形機等之成形裝置來成形為指定的形狀。 Recently, the demand for fluorine-based resin molded articles such as protective sheets for solar battery modules and water treatment filters has been increasing year by year. The fluorine-based resin component is molded into a predetermined shape by using a molding apparatus such as an extruder or an injection molding machine.
對於處於壓出成形機的料筒等之樹脂成形機的熔融樹脂環境下之零件，有要求高耐磨耗性之情況，如此的零件例如使用如與本案申請人同一人之日本發明專利第4121694號公報(JP 4121694B2)(以下在本說明書中稱為「專利文獻1」)中記載之燒結體Ni基底金屬陶瓷。 For a part in a molten resin environment of a resin molding machine such as a cylinder of an extrusion molding machine, there is a demand for high wear resistance, and such a part is, for example, a Japanese invention patent No. 4121694 which is the same as the applicant of the present application. A sintered Ni-based cermet described in Japanese Patent Publication No. JP-A No. 4121694B2 (hereinafter referred to as "Patent Document 1").
然而，於氟系樹脂之成形時，氟系樹脂會分解而產生腐蝕性氣體(含氟的氣體)，此時即使本來具有高耐蝕耐磨耗性之Ni基底金屬陶瓷，也有早期損耗之情況。 However, in the molding of the fluorine-based resin, the fluorine-based resin is decomposed to generate a corrosive gas (fluorine-containing gas). In this case, even the Ni-based cermet having high corrosion resistance and wear resistance may have early loss.
為了防止或抑制腐蝕損耗，考慮使用高耐蝕性Ni基底合金的Hastelloy C(商標)或由KUBOTA股份有限公司所提供之CH-501材料。Hastelloy C係由HAYNES公司(美國)所提供之Ni-Mo-Cr系耐蝕合金，雖然耐蝕性優異，但硬度低，耐磨耗性差。CH-501為Ni基底金屬陶瓷，特徵為形成微細的組織，但必須藉由HIP之燒結，高的製造成本係成為問題。即，使用上述眾所周知的材料 時，可減低因腐蝕所造成的材料損耗，但耐磨耗性不充分而且為低壽命，或有零件製造成本(例如料筒的製造單價)變高之問題。 In order to prevent or suppress corrosion loss, it is considered to use Hastelloy C (trademark) of a high corrosion-resistant Ni base alloy or CH-501 material supplied by KUBOTA Co., Ltd. Hastelloy C is a Ni-Mo-Cr corrosion-resistant alloy supplied by HAYNES (USA). Although it has excellent corrosion resistance, it has low hardness and poor wear resistance. CH-501 is a Ni-based cermet characterized by the formation of a fine structure, but it must be sintered by HIP, and high manufacturing cost is a problem. That is, using the well-known materials described above In time, the material loss due to corrosion can be reduced, but the wear resistance is insufficient and the life is low, or the manufacturing cost of the parts (for example, the unit price of the barrel) becomes high.
本發明之目的在於以低成本提供即使在氟系氣體等之腐蝕性氣體存在的環境下，也具有充分的耐蝕性及耐磨耗性之Ni基底耐蝕耐磨耗合金。 An object of the present invention is to provide a Ni-base corrosion-resistant and wear-resistant alloy which has sufficient corrosion resistance and wear resistance even in an environment in which a corrosive gas such as a fluorine-based gas exists in a low cost.
本發明係以專利文獻1(JP 4121694B2)的合金作為基礎，主要藉由謀求Cu添加及Mo/B比之最合適化，不犠牲耐磨耗性而謀求耐蝕性之提高。 According to the alloy of Patent Document 1 (JP 4121694B2), the present invention mainly seeks to improve the corrosion resistance without sacrificing wear resistance by optimizing the Cu addition and the Mo/B ratio.
於本發明合金中，沿襲藉由韌性優異的金屬結合相來結合已集合成球狀或塊狀的微細之硬質粒子的集合體，不使耐磨耗性而降低而謀求韌性的提高之專利文獻1(JP 4121694B2)之合金組織。於本發明合金中，與專利文獻1的合金比較下，除了藉由增加金屬結合相中的Mo固溶量，還使所添加的Cu固溶於金屬結合相中，藉此增大金屬結合相進而合金全體之耐蝕性。達成耐蝕性的增大係沒有像Hastelloy C那麼犠牲耐磨耗性。 In the alloy of the present invention, it is possible to combine an aggregate of fine hard particles which have been aggregated into a spherical shape or a block shape by a metal bond phase having excellent toughness, and to improve the toughness without lowering the abrasion resistance. Alloy structure of 1 (JP 4121694B2). In the alloy of the present invention, in addition to the alloy of Patent Document 1, in addition to increasing the amount of solid solution of Mo in the metal-binding phase, the added Cu is solid-dissolved in the metal-binding phase, thereby increasing the metal-bound phase. Further, the corrosion resistance of the entire alloy. The increase in corrosion resistance is not as good as Hastelloy C.
本發明的合金具體地，係全體的合金組織含有Si、Mo、Cu固溶於Ni中之結合相(a)(金屬結合層)，與 分散於前述結合相(a)中的球狀或塊狀之硬質物集合體(b)而成，硬質物集合體(b)的金屬組織係含有與前述結合相(a)同樣之Si、Mo、Cu固溶於Ni中之結合相(c)，與分散於此結合層(c)中之由Mo2NiB2及Ni3B等的硼化物所成之分散層(d)而成(參照圖1、圖2)。於本發明合金中，與成為基礎的專利文獻1之合金同樣地，硬質物集合體(b)之大小較佳為30~300μm左右。 Specifically, the alloy of the present invention contains the entire alloy structure containing Si, Mo, Cu, a binder phase (a) (metal bond layer) which is solid-dissolved in Ni, and a spherical or block dispersed in the above-mentioned binder phase (a). The hard material aggregate (b) is formed, and the metal structure of the hard material aggregate (b) contains a binding phase (c) in which Si, Mo, and Cu are dissolved in Ni in the same manner as the above-mentioned bonded phase (a). The dispersion layer (d) made of a boride such as Mo 2 NiB 2 or Ni 3 B dispersed in the bonding layer (c) is formed (see FIGS. 1 and 2 ). In the alloy of the present invention, the size of the hard aggregate (b) is preferably about 30 to 300 μm, similarly to the alloy of Patent Document 1 which is the basis.
本發明合金之製造時所用的原料粉末，例如係使用熔化有NiB、Si、Mo、Ni、Cu之熔液，藉由噴散法(熔液噴霧法)來製造者，具有以下之組成，含有B：2.2~3.0%、Si：3.0~5.0%、Mo：18~25%、Cu：1~15%，剩餘部分由Ni及無可避免的雜質所構成，Mo含量對B含量的重量比為7~9。較佳為在噴散粉末之中，使用以規定網目的篩子所篩選之粒徑30~300μ者作為原料粉末。藉由噴散(atomize)法來製造本發明合金的原料粉末，可得到具有在Si、Mo、Cu固溶於Ni中之結合相中，分散有由Mo2NiB2及Ni3B等的硼化物所成之硬質粒子的金屬組織之粉末，藉由將此粉末燒結，而得到具有Si、Mo、Cu固溶於Ni中之結合相(上述的結合相(a)(c))之燒結合金，此燒結合金(本發明合金)係顯示優異的耐蝕性。相對於其，例如藉由粉碎法來製作原料粉末時，生成NiSiMo化合物，此NiSiMo化合物存在時，確認燒結合金的耐蝕性降低。再者，於燒結原料粉末時，合適為藉由真空燒結法及熱靜水加壓法等來進行成形。 The raw material powder used in the production of the alloy of the present invention is produced by, for example, a melt solution of NiB, Si, Mo, Ni, and Cu, which is produced by a spray method (melt spray method), and has the following composition and contains B: 2.2~3.0%, Si: 3.0~5.0%, Mo: 18~25%, Cu: 1~15%, the remainder is composed of Ni and inevitable impurities, and the weight ratio of Mo content to B content is 7~9. It is preferable to use, as a raw material powder, a particle size of 30 to 300 μ which is sieved by a sieve of a predetermined mesh among the powders to be dispersed. The raw material powder of the alloy of the present invention is produced by an atomization method, and a boron having a solid solution of Si, Mo, and Cu in Ni is obtained, and boron such as Mo 2 NiB 2 and Ni 3 B is dispersed. a powder of a metal structure of a hard particle formed by the compound, and sintering the powder to obtain a sintered alloy having a binding phase in which Si, Mo, and Cu are solid-dissolved in Ni (the above-described bonded phase (a) (c)) This sintered alloy (the alloy of the present invention) exhibits excellent corrosion resistance. With respect to this, for example, when a raw material powder is produced by a pulverization method, a NiSiMo compound is formed, and when the NiSiMo compound is present, it is confirmed that the corrosion resistance of the sintered alloy is lowered. Further, in the case of sintering the raw material powder, it is suitably formed by a vacuum sintering method, a hot hydrostatic press method, or the like.
本發明合金的組成係以重量%計含有B：2.2~3.0%、Si：3.0~5.0%、Mo：18~25%、Cu：1~15%，剩餘部分由Ni及無可避免的雜質所構成。又，Mo含量對B含量的重量比為7~9。再者，從燒結性提高之觀點來看，燒結前的粉末較佳為含有以重量%計C：0.01~0.5%，但亦可未必進行C添加。再者，以下在本說明書中，表示組成或含量的百分率，只要沒有特別附加說明，則皆意味重量%。 The composition of the alloy of the present invention contains B: 2.2 to 3.0%, Si: 3.0 to 5.0%, Mo: 18 to 25%, Cu: 1 to 15% by weight, and the balance is Ni and inevitable impurities. Composition. Further, the weight ratio of the Mo content to the B content is 7 to 9. Further, from the viewpoint of improvement in sinterability, the powder before sintering preferably contains C: 0.01 to 0.5% by weight, but may not necessarily be added with C. In the following description, the percentages indicating the composition or content mean weight % unless otherwise specified.
以下，個別地說明進行上述之成分規定的理由。 Hereinafter, the reason for performing the above-described component specification will be individually described.
Mo係固溶於結合相(前述的結合相(a)、(c))中，提高合金的耐蝕性。Mo含量未達18%時，固溶於結合相中的Mo量變少，無法得到充分的耐蝕性提高效果。 又，Mo含量超過25%時，為了得到健全的燒結體，必須提高燒結溫度，導致製造成本之增大。 Mo is solid-solubilized in the binding phase (the aforementioned binding phases (a), (c)) to improve the corrosion resistance of the alloy. When the Mo content is less than 18%, the amount of Mo dissolved in the binder phase is small, and sufficient corrosion resistance improving effect cannot be obtained. Moreover, when the Mo content exceeds 25%, in order to obtain a sound sintered body, it is necessary to increase the sintering temperature and increase the manufacturing cost.
B係與Ni及Mo一起形成硬質粒子之硼化物(Mo2NiB2)，提高合金的耐磨耗性。B含量未達2.2%時，所生成的Mo2NiB2量變少，耐磨耗性降低(惟，由於固溶於結合相中的Mo增加，耐蝕性係隨著其而稍微升高)。B含量超過3.0%時，隨著Mo2NiB2的發生，若沒有增加Mo含量，則固溶於結合相中的Mo係減少，耐蝕性會變差。然而，如前述，增加Mo含量時，必須提高燒結溫度，製造成本(燒結成本)會增大。因此，B含量為2.2~3.0%。 The B system forms a boride (Mo 2 NiB 2 ) of hard particles together with Ni and Mo to improve the wear resistance of the alloy. When the B content is less than 2.2%, the amount of Mo 2 NiB 2 formed is small, and the abrasion resistance is lowered (however, since the Mo dissolved in the binder phase is increased, the corrosion resistance is slightly increased with it). When the B content exceeds 3.0%, the Mo content in the solid phase is reduced and the corrosion resistance is deteriorated without increasing the Mo content as the Mo 2 NiB 2 is generated. However, as described above, when the Mo content is increased, the sintering temperature must be increased, and the manufacturing cost (sintering cost) is increased. Therefore, the B content is 2.2 to 3.0%.
如前述，本發明合金係除了增加結合相中的Mo固溶量，還使所添加的Cu固溶於結合相中，藉此增大結合相 進而合金全體之耐蝕性。如由上述B含量之說明可知，合金中所含有的Mo之一部分由於對應於B含量生成Mo2NiB2而被消耗，殘餘的Mo係固溶於結合相中而存在。考慮上述者，為了成為看得到耐蝕性的提高之程度，Mo含量對B含量的重量比(Mo/B重量比)必須為7以上。另一方面，如前述，藉由噴散法所製作的原料粉末，雖然具有在Si、Mo、Cu固溶於Ni中之結合相中，分散有由Mo2NiB2及Ni3B等的硼化物所成之硬質粒子的金屬組織，但Mo若大量地固溶於此粉末的結合相中，則為了得到健全的組織，發生所需要的燒結溫度變高之問題。因此，Mo/B重量比為9以下。 As described above, in addition to increasing the amount of Mo solid solution in the binder phase, the alloy of the present invention also solidifies the added Cu in the binder phase, thereby increasing the corrosion resistance of the binder phase and thus the entire alloy. As is apparent from the above description of the B content, one part of Mo contained in the alloy is consumed by generating Mo 2 NiB 2 in accordance with the B content, and the residual Mo is solid-dissolved in the binder phase. In view of the above, in order to improve the corrosion resistance, the weight ratio of the Mo content to the B content (Mo/B weight ratio) must be 7 or more. On the other hand, as described above, the raw material powder produced by the scattering method has boron in which Mo 2 NiB 2 and Ni 3 B are dispersed in a bonded phase in which Si, Mo, and Cu are solid-dissolved in Ni. The metal structure of the hard particles formed by the compound, but if Mo is largely dissolved in the binder phase of the powder, the required sintering temperature becomes high in order to obtain a sound structure. Therefore, the Mo/B weight ratio is 9 or less.
Cu係與Mo同樣地，藉由固溶於結合相中而提高合金的耐蝕性。Cu含量若未達2%，則固溶於結合相中的Cu量少，不出現耐蝕性提高效果。另一方面，Cu含量若超過15%，則生成Cu系化合物而使合金之耐蝕性降低。再者，Cu含量若超過15%，則韌性降低，容易產生微細的缺隙，結果低磨耗性降低。因此，Cu含量為1~15%。再者，若重視耐磨耗性，則Cu添加量較佳為10%以下。 Similarly to Mo, Cu is improved in corrosion resistance of the alloy by solid solution in the binder phase. If the Cu content is less than 2%, the amount of Cu dissolved in the binder phase is small, and the effect of improving corrosion resistance does not occur. On the other hand, when the Cu content exceeds 15%, a Cu-based compound is formed to lower the corrosion resistance of the alloy. In addition, when the Cu content exceeds 15%, the toughness is lowered, and fine voids are likely to occur, and as a result, low attrition property is lowered. Therefore, the Cu content is 1 to 15%. Further, when the wear resistance is important, the Cu addition amount is preferably 10% or less.
Si係具有降低燒結溫度之作用。Si含量未達3.0%時，不充分得到燒結溫度的降低效果。另一方面，Si含量超過5.0%時，由於容易生成使合金的韌性降低之NiSi化合物及使合金的耐蝕性降低之NiSiMo化合物而不宜。因此，Si含量為3.0~5.0%。 The Si system has a function of lowering the sintering temperature. When the Si content is less than 3.0%, the effect of lowering the sintering temperature is not sufficiently obtained. On the other hand, when the Si content is more than 5.0%, it is not preferable to form a NiSi compound which lowers the toughness of the alloy and a NiSiMo compound which lowers the corrosion resistance of the alloy. Therefore, the Si content is 3.0 to 5.0%.
C具有將粉末表面的氧化膜還原，降低噴散粉末之燒 結溫度之效果。C含量(添加量)為0.01%以下時，將粉末表面的氧化膜還原之效果小，得不到充分的燒結溫度降低效果。C含量為0.5%以上時，碳化物析出許多，使強度、高溫耐蝕性變差。因此，添加C時，添加量為0.01~0.5%。再者，雖然較佳為添加C者，但取決於噴散粉末的製造條件等，粉末表面的氧化程度亦有小的情況，此時盡量減少C之添加。於C之添加方法中，考慮2個方法，其為於噴散粉末即噴霧粉的原料之溶解時，預先添加C後，進行噴霧之方法，與溶解如以往之不含有C的原料，將噴散粉末純化，於其中添加C(石墨)之方法。於任一方法中，皆可藉由所添加的C來充分還原粉末表面的氧化物，提高噴散粉末之燒結性。尚且，如前者在原料溶解時添加C時，C可單獨添加，也可藉由添加Mo、Si、B等之碳化物來添加C，任一情況皆得到同樣的效果。 C has the effect of reducing the oxide film on the surface of the powder and reducing the burning of the powder. The effect of junction temperature. When the C content (addition amount) is 0.01% or less, the effect of reducing the oxide film on the surface of the powder is small, and a sufficient effect of lowering the sintering temperature cannot be obtained. When the C content is 0.5% or more, the carbide precipitates a lot, and the strength and high-temperature corrosion resistance are deteriorated. Therefore, when C is added, the addition amount is 0.01 to 0.5%. Further, although it is preferable to add C, depending on the production conditions of the powder to be sprayed, etc., the degree of oxidation of the surface of the powder is also small, and at this time, the addition of C is minimized. In the method of adding C, two methods are considered, which are to dissolve the raw material of the spray powder, that is, to dissolve the raw material of the spray powder, and then to spray the method, and to dissolve the raw material which does not contain C as in the prior art. The powder was purified and a method of adding C (graphite) thereto. In either method, the oxide on the surface of the powder can be sufficiently reduced by the added C to improve the sinterability of the sprayed powder. Further, when the former is added with C when the raw material is dissolved, C may be added alone, or C may be added by adding a carbide such as Mo, Si, or B, and the same effect can be obtained in either case.
本發明合金係可適用於塑膠成形機之與熔融塑膠(尤其含氟的塑膠)接觸的零件，例如料筒、螺桿等。再者，本發明合金由於比較高價，與其由本發明合金來構成一個零件的全體，倒不如較佳為僅將與熔融樹脂接觸的部分設置在基材(通常由鋼鐵材料或鑄鐵所構成)上作為襯裏設置。參照圖3，簡單地說明製法。圖3中，1為筒狀體，2為棒狀體，3為上下之蓋體，4為填充於筒狀體1與棒狀體2之間的原料粉末。於此狀態下，藉由在筒狀體1的表面或棒狀體2的表面、蓋體3的表面，塗佈脫模劑，於指定溫度進行燒結，而得到筒狀體1(或棒狀體2)與原料 粉末4(原料粉末4的燒結體)所一體化之構造體。筒狀體1例如可成為料筒的基材(由鋼鐵材料或鑄鐵所構成)。又，棒狀體2例如可成為螺桿的基材(由鋼鐵材料所構成)。再者，作為在基材表面上形成燒結體(燒結層)用之燒結模具或燒結夾具之形態，例如可利用本案申請人的專利申請案之日本發明專利公開公報JP4-202705A(及對應美國專利公報US 5,336,527及對應德國公開公報DE 4139421A)中所揭示者。US 5,336,527係藉由參照而併入本說明書中。 The alloy of the present invention can be applied to parts of a plastic molding machine that are in contact with molten plastics (especially fluorine-containing plastics), such as a cylinder, a screw, and the like. Further, since the alloy of the present invention is relatively expensive, it is preferable that only the portion in contact with the molten resin is provided on the substrate (usually composed of steel material or cast iron) as the entire part of the alloy of the present invention. Lining set. Referring to Fig. 3, the manufacturing method will be briefly explained. In Fig. 3, 1 is a cylindrical body, 2 is a rod-shaped body, 3 is a top and bottom cover, and 4 is a raw material powder filled between the cylindrical body 1 and the rod-shaped body 2. In this state, the release agent is applied to the surface of the cylindrical body 1, the surface of the rod 2, and the surface of the lid 3, and sintered at a predetermined temperature to obtain a cylindrical body 1 (or a rod shape). Body 2) and raw materials A structure in which the powder 4 (a sintered body of the raw material powder 4) is integrated. The tubular body 1 can be, for example, a base material (consisting of steel material or cast iron) of the cylinder. Further, the rod 2 can be, for example, a base material of a screw (made of a steel material). In addition, as a form of a sintering mold or a sintering jig for forming a sintered body (sintered layer) on the surface of the substrate, for example, Japanese Patent Laid-Open Publication No. JP4-202705A (and corresponding US patent) of the present applicant's patent application is available. The one disclosed in the publication US Pat. No. 5,336,527 and the corresponding German publication No. DE 4139421 A. US 5,336,527 is incorporated herein by reference.
與專利文獻1之合金比較下，本發明合金係高價的Mo之含量增加。但是，由於添加比Ni便宜的Cu，隨著與Cu添加量相應的部分，高價的Ni之含量係減少。因此，材料成本係與專利文獻1的合金大約同等。又，本發明合金的噴散處理費用係與專利文獻1記載的合金同等。再者，與專利文獻1的合金比較下，本發明合金係可在(雖然稍高)沒有大幅改變的燒結溫度下製造，由於燒結時的收縮量亦與專利文獻1的合金沒有不同，可藉由相同的生產設備來製造構件。即，使用本發明合金時，能以與專利文獻1的合金同樣之總費用來製造構件。 Compared with the alloy of Patent Document 1, the alloy of the present invention has an increased content of Mo which is expensive. However, since Cu which is cheaper than Ni is added, the content of expensive Ni is decreased as a part corresponding to the amount of addition of Cu. Therefore, the material cost is approximately the same as that of the alloy of Patent Document 1. Further, the discharge treatment cost of the alloy of the present invention is equivalent to the alloy described in Patent Document 1. Further, in comparison with the alloy of Patent Document 1, the alloy of the present invention can be produced at a sintering temperature which is not greatly changed (albeit slightly higher), and the amount of shrinkage at the time of sintering is not different from that of the alloy of Patent Document 1, and can be borrowed. The components are manufactured from the same production equipment. That is, when the alloy of the present invention is used, the member can be manufactured at the same total cost as the alloy of Patent Document 1.
以下，以具體的實施例為基礎，更詳細說明本發明。 Hereinafter, the present invention will be described in more detail based on specific examples.
如下表1之上段中後示，製作試料編號1~8之8種類的試料。再者，於下表1中，所謂的「習知材料」，就 是意味具有專利文獻1(JP 4121694B2)的合金組成之合金，而且所謂的「Mo/B」，就是意味以重量比計的Mo含量/B含量之值。另外，對於試料編號1~4、7、8，皆添加0.1%的C(碳)。表中的「燒結溫度」係藉由實驗求得能得到空穴不存在的健全之燒結組織的最低溫度。對上述各試料，進行腐蝕試驗及磨耗試驗。於腐蝕試驗中，將4×7×25mm的長方體之試驗片浸漬在50℃的10%氫氟酸中24小時，測定腐蝕減量。於磨耗試驗中，對於由直徑8mm的銷所成之試驗片，藉由高千穗精機製的盤上銷磨耗試驗機，在荷重1000N、摩擦速度0.2m/sec、摩擦距離400m之條件下測定磨耗減量。下表1的下段中顯示其結果。 As shown in the upper part of Table 1 below, samples of 8 types of sample numbers 1 to 8 were prepared. Furthermore, in Table 1 below, the so-called "known materials" It is an alloy having an alloy composition of Patent Document 1 (JP 4121694B2), and the so-called "Mo/B" means a value of Mo content/B content by weight ratio. In addition, 0.1% of C (carbon) was added to sample numbers 1 to 4, 7, and 8. The "sintering temperature" in the table is obtained by experiments to obtain the lowest temperature at which a sintered sintered structure in which voids are not present can be obtained. Each of the above samples was subjected to a corrosion test and an abrasion test. In the corrosion test, a test piece of a rectangular parallelepiped of 4 × 7 × 25 mm was immersed in 10% hydrofluoric acid at 50 ° C for 24 hours, and the corrosion loss was measured. In the abrasion test, for the test piece made of a pin having a diameter of 8 mm, the wear reduction was measured under the conditions of a load of 1000 N, a friction speed of 0.2 m/sec, and a friction distance of 400 m by a pin-on-pin wear tester with a high-precision mechanism. . The results are shown in the lower section of Table 1 below.
如由上述表1的下段可知，與習知合金(試料編號1、3)比較下，本發明合金(試料編號7、8)係大幅提高對氫氟酸的耐蝕性(對氟系氣體的耐蝕性之指標)，即使與以往可使用在腐蝕損耗成為問題之部位的合金(試料編號5、6)比較下，也具有同等的耐蝕性。與習知合金(試料編號1、3)比較下，本發明合金(試料編號7、8)雖然耐磨耗性有稍微降低的傾向，但與以往可使用在腐蝕損耗成為問題之部位的合金(試料編號5、6)比較下，耐磨耗性係大幅提高。即，可知以本發明合金，可一邊實現對氫氟酸的耐蝕性之提高，一邊將耐磨耗性的降低抑制在最 小限度。 As can be seen from the lower part of the above Table 1, the alloy of the present invention (sample Nos. 7 and 8) greatly improved the corrosion resistance to hydrofluoric acid (corrosion resistance to fluorine-based gas) compared with the conventional alloy (sample Nos. 1 and 3). The index of the properties is equivalent to the conventional alloy (sample Nos. 5 and 6) in which corrosion loss is a problem, and has the same corrosion resistance. In comparison with the conventional alloys (sample Nos. 1 and 3), the alloys of the present invention (sample Nos. 7 and 8) tend to have a slight decrease in wear resistance, but an alloy which is a site where corrosion loss is a problem can be used conventionally ( In comparison with sample No. 5 and 6), the wear resistance was greatly improved. In other words, it is understood that the alloy of the present invention can reduce the corrosion resistance at the same time while improving the corrosion resistance of hydrofluoric acid. Small limit.
再者，若比較本發明合金(試料編號7、8)彼此，則Cu量高的試料編號7雖然耐蝕性稍微優異，但耐磨耗性稍差。 In addition, when the alloys of the present invention (sample Nos. 7 and 8) were compared with each other, the sample No. 7 having a high Cu amount was slightly excellent in corrosion resistance, but the abrasion resistance was slightly inferior.
上述表1的下段之「料筒製造比率」，就是以使用專利文獻1的合金(習知材料)之情況為基準(=1)，以比率來表示用於製造樹脂壓出成形機的料筒之製造成本者。本發明合金之試料編號7、8係可用與習知材料同等的製造成本來製造。與本發明合金具有同等組成但粉末製法不同的試料編號4之合金，由於燒結時的收縮大，在與燒結同時地接合於鋼鐵基材者係非常困難(即，作為工業的生產方法不實際的)。本發明合金係與專利文獻1的合金(習知材料)同樣地，使用藉由熔液噴霧法所製造之原料粉末(噴散粉末)，如此的原料粉末係燒結時的收縮少，在與燒結同時地接合於鋼鐵基材者係容易。因此，可以低成本製造經Ni基底耐蝕耐磨耗合金所被覆之料筒。又，試料編號5、6的合金，由於在與燒結同時地接合於鋼鐵基材者為困難，或需要特別的燒結方法(HIP)，而製造成本變高。 The "cylinder manufacturing ratio" in the lower part of the above-mentioned Table 1 is a cylinder for manufacturing a resin extrusion molding machine in a ratio based on the case of using the alloy (a conventional material) of Patent Document 1 (=1). The cost of manufacturing. The sample numbers 7 and 8 of the alloy of the present invention can be produced at the same manufacturing cost as conventional materials. The alloy of sample No. 4 having the same composition as the alloy of the present invention but having a different powder preparation method has a large shrinkage during sintering, and is very difficult to bond to a steel substrate at the same time as sintering (that is, it is not practical as an industrial production method). ). In the alloy of the present invention, similarly to the alloy (known material) of Patent Document 1, a raw material powder (dissolved powder) produced by a melt spray method is used, and such a raw material powder has less shrinkage during sintering, and is sintered. It is easy to join the steel substrate at the same time. Therefore, the cylinder covered with the Ni-base corrosion-resistant and wear-resistant alloy can be manufactured at low cost. Further, in the alloys of Sample Nos. 5 and 6, it is difficult to join the steel substrate at the same time as sintering, or a special sintering method (HIP) is required, and the manufacturing cost is high.
a‧‧‧結合相 A‧‧‧ combination phase
b‧‧‧硬質物集合體 B‧‧‧hard mass aggregate
c‧‧‧結合相 c‧‧‧Combined phase
d‧‧‧分散層 d‧‧‧Dispersion layer
1‧‧‧筒狀體 1‧‧‧Cylinder
2‧‧‧棒狀體 2‧‧‧ rods
3‧‧‧蓋體 3‧‧‧ cover
4‧‧‧原料粉末 4‧‧‧Material powder
圖1係說明本發明合金的合金組織用之模型圖。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a model diagram showing the alloy structure of the alloy of the present invention.
圖2係顯示本發明合金的合金組織之電子顯微鏡照片(二次電子線影像)之影本。 Fig. 2 is a view showing an electron microscope photograph (secondary electron beam image) of the alloy structure of the alloy of the present invention.
圖3係說明在燒結時將本發明合金與基材一體化之方法之示意圖。 Figure 3 is a schematic view showing a method of integrating the alloy of the present invention with a substrate at the time of sintering.
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| SU293871A1 (en) * | 1969-03-18 | 1971-01-26 | А. Б. Альтман, Н. С. Брунова, П. А. Гладышев, Т. А. Козлова | METAL CERAMIC NONMAGNETIC ALLOY |
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| JPS6479338A (en) * | 1987-06-03 | 1989-03-24 | Kobe Steel Ltd | Wear-resistant alloy excellent in corrosion resistance to halogen gas and its production |
| JPH0762201B2 (en) * | 1988-03-24 | 1995-07-05 | 株式会社神戸製鋼所 | Wear-resistant powder-sintered alloy with excellent corrosion resistance |
| JP4121694B2 (en) * | 2000-08-30 | 2008-07-23 | 東芝機械株式会社 | Sintered body Ni-based cermet and parts for plastic molding machine and die casting machine using the same |
| JP2004034071A (en) | 2002-07-02 | 2004-02-05 | Toshiba Mach Co Ltd | Injection unit of die-casting machine |
| JP2004176136A (en) * | 2002-11-27 | 2004-06-24 | Toshiba Mach Co Ltd | Method of producing corrosion resistant and wear resistant material |
| JP4354315B2 (en) * | 2004-03-22 | 2009-10-28 | 東芝機械株式会社 | Aluminum melt contact member and method of manufacturing the same |
| EP1777313B1 (en) * | 2004-06-30 | 2012-08-01 | Sumitomo Metal Industries, Ltd. | Ni BASE ALLOY MATERIAL TUBE AND METHOD FOR PRODUCTION THEREOF |
| JP4499024B2 (en) * | 2005-12-02 | 2010-07-07 | 東芝機械株式会社 | Hot water supply pipe for aluminum die casting and method for manufacturing the same |
| KR102309630B1 (en) | 2018-09-10 | 2021-10-05 | 주식회사 엘지에너지솔루션 | ICB assembly, battery module comprising the same and method for fabricating the battery module |
-
2012
- 2012-09-26 WO PCT/JP2012/074749 patent/WO2013058074A1/en active Application Filing
- 2012-09-26 DE DE112012004408.8T patent/DE112012004408T5/en active Pending
- 2012-09-26 KR KR1020147010129A patent/KR101701012B1/en active IP Right Grant
- 2012-09-26 CN CN201280050993.2A patent/CN103874774B/en active Active
- 2012-09-26 JP JP2013539592A patent/JP5882351B2/en active Active
- 2012-09-26 US US14/353,018 patent/US20140245863A1/en not_active Abandoned
- 2012-10-19 TW TW101138679A patent/TWI460282B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103874774B (en) | 2016-12-07 |
| KR20140078666A (en) | 2014-06-25 |
| US20140245863A1 (en) | 2014-09-04 |
| WO2013058074A1 (en) | 2013-04-25 |
| KR101701012B1 (en) | 2017-01-31 |
| TWI460282B (en) | 2014-11-11 |
| DE112012004408T5 (en) | 2014-08-07 |
| JP5882351B2 (en) | 2016-03-09 |
| CN103874774A (en) | 2014-06-18 |
| JPWO2013058074A1 (en) | 2015-04-02 |
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