1316956 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種粉末金屬組合物。本發明明確關於— 種包括含至少一種二級醯胺之潤滑劑及/或黏著劑之粉末 金屬組合物。本發明進一步關於一種製造坯體之方法、製 造經黏著以鐵為之粉末組合物之方法及該潤滑劑及/或黏 著劑之用途。 【先前技術】1316956 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a powder metal composition. The present invention is expressly directed to a powder metal composition comprising a lubricant and/or an adhesive comprising at least one secondary guanamine. The invention further relates to a method of making a blank, a method of making a powdered composition of iron, and the use of the lubricant and/or adhesive. [Prior Art]
金屬粉末在工業上可用於製造金屬產物，該金屬產物製 造係藉由，在模中於高壓下緊壓金屬粉末，使緊壓物脫 杈，並視需要燒結該產物。在大多數粉末冶金應用 中’為在緊壓期間於粉末顆粒之間及在自模脫模期間於模 和緊壓物之間提供必要湖滑作用，在粉末中包含潤滑劑。、 由在金屬粉末中包含的满滑劑取得的爛滑作用被稱為内部 潤滑’與此對比，外部潤滑作用藉由施加潤滑劑到且中緊 壓粉末之模壁而取得。在脫模期間潤滑作用不足導致在緊 壓物和模間的過度摩擦作用，產 ’、 面及產物表面。 i錢“以損害模表 門邵潤潸作用藉由用特殊潤滑劑取得 劑與粉末狀鐵或以鐵為主之粉末混合。 於使添加劑(例如，合金元素 广劑亦可用 粒。在此等例中，~ π 鐵或以鐵為主之顆 Jψ潤滑劑因此作為黏著劍，* + 理期‘間降少或消除添加劑分離。 並在運輸及處 金屬名常用於m應用所用之潤 " 如鋰和鋅硬脂酸 I05083.doc 1316956 用此類型;Γ4滑劑的缺點為，由於在燒結期間自潤滑 劑釋放金屬，满滑劑中的金屬氧化物污染燒結爐的内側。 另門題為’在燒結後於元件上生成銹斑。另一種常用潤 月劑為伸乙基雙硬脂酿胺（EBS)。在使用此潤滑劑時，在 燒、。後亦可鲍在元件上生成銹斑，但與使用（例如）硬脂酸 辞比車乂程度較小。由於潤滑劑強烈影響金屬粉末之緊壓及 燒生質所用潤滑劑之量、組合物和結構最佳化對獲得 门及致费度和所產生零件優良表面光潔度至關重要。 【發明内容】 本發明一個目的為提供一種新粉末金屬組合物，該組合 物包括減少或消除利用高脫模力之問題及經燒結零件之生 鏽表面之潤滑劑及/或黏著劑。 本發明另一目的為提供一種製造緊壓產物和經燒結或熱 處理之零件之方法、製造經黏著粉末金屬組合物之方法以 及該潤滑劑及/或黏著劑之用途。 此等目的藉由一種粉末金屬組合物達到，該組合物包括 一種以鐵為主之粉末和含至少一種二級醯胺之潤滑劑及/ 或黏著劑。本發明進一步關於一種藉由上述組合物經過緊 壓而製造坯體之方法。 製造經黏著粉末金屬組合物之方法包括：混合一種以鐵 為主之粉末與至少一種二級醯胺，並將混合物加熱到高於 該至少一種二級醯胺之熔點之溫度。 此外，本發明關於至少一種二級醯胺作為潤滑及/或黏 著劑用於以鐵為主之粉末之用途及其用於模壁潤滑之用 105083.doc 1316956 途。 【實施方式】 根據本發明之粉末金屬組合物中的潤滑劑及/或黏著劑 • 為至少一種可由以下通式界定之二級醯胺： R!-NH-CO-R2 其中Ri-和R2-基團可相同或不同，為直鏈或分支、飽和 或不飽和脂族煙基。 R!和R2較佳獨立包括1 〇至24個碳原子。 ® Ri和R2較佳選自由炫基和烯基所組成之群組。 烷基可選自癸基、十一烷基、十二烷基、十三烷基、十 四烷基、十五烷基'十六烷基、十七烷基、十八烷基、十 九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷 基、二十四烷基。 烯基可選自癸烯基、十一碳烯基、十二碳烯基、十三碳 稀基、十四碳烯基、十五碳烯基、十六碳烯基、十七碳烯 鲁 基、十八碳烯基、十九碳烯基、二十碳烯基、二十一碳烯 基、二十二碳烯基、二十三碳烯基、二十四碳烯基。 較佳一級醯胺之實例顯示於表1中。 105083.doc 1316956Metal powders are industrially useful in the manufacture of metal products by compacting the metal powder under high pressure in a mold, de-squeezing the compact, and sintering the product as needed. In most powder metallurgy applications, the necessary lake slip is provided between the mold and the compact during the compaction between the powder particles and during the demolding of the mold, and the lubricant is contained in the powder. The squeaking effect obtained by the slip agent contained in the metal powder is referred to as internal lubrication. In contrast, the external lubrication is obtained by applying a lubricant to and compressing the mold wall of the powder. Insufficient lubrication during demolding results in excessive friction between the compact and the mold, producing surfaces, surfaces and products. i money "by damaging the mold door Shao Run 潸 effect by mixing with a powdered iron or iron-based powder with a special lubricant acquisition agent. For additives (for example, alloying elements can also be used for granules. In these cases, ~ π iron or iron-based J ψ lubricant is therefore used as a sticky sword, * + ration period 'minus drop or eliminate additive separation. And in the transportation and metal name commonly used in m applications of the run " such as lithium and Zinc stearic acid I05083.doc 1316956 is of this type; the disadvantage of Γ4 slip agent is that the metal oxide in the slip agent contaminates the inside of the sintering furnace due to the release of metal from the lubricant during sintering. After the rust is formed on the component, another commonly used lunar agent is Ethyl Ethyl Esteramine (EBS). When using this lubricant, after burning, the abalone can also form rust on the component, but with (for example) stearic acid is less pronounced than rutting. Because the lubricant strongly influences the compaction of the metal powder and the amount of lubricant used in the burning of the biomass, the composition and structure are optimized to obtain the door and the cost and the Produce excellent surface finish of parts SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel powder metal composition comprising a lubricant and/or an adhesive which reduces or eliminates the problem of utilizing high mold release forces and the rusted surface of the sintered part. Another object of the present invention is to provide a method of making a compacted product and a sintered or heat treated part, a method of making an adhesive powder metal composition, and the use of the lubricant and/or adhesive. The powder metal composition is attained, the composition comprising an iron-based powder and a lubricant and/or an adhesive comprising at least one secondary guanamine. The invention further relates to a preform produced by compacting the above composition The method of making an adherent powder metal composition comprises: mixing an iron-based powder with at least one secondary guanamine, and heating the mixture to a temperature above the melting point of the at least one secondary guanamine. Furthermore, the invention relates to the use of at least one secondary guanamine as a lubricating and/or adhesive for iron-based powders and for use in mold walls Lubricating 105083.doc 1316956. [Embodiment] The lubricant and/or adhesive in the powder metal composition according to the present invention is at least one secondary guanamine which can be defined by the following formula: R!-NH- CO-R2 wherein the Ri- and R2- groups may be the same or different and are straight-chain or branched, saturated or unsaturated aliphatic nicotine groups. R! and R2 preferably independently comprise from 1 to 24 carbon atoms. R2 is preferably selected from the group consisting of a leukoyl group and an alkenyl group. The alkyl group may be selected from the group consisting of decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl 'ten Hexaalkyl, heptadecyl, octadecyl, nonadecyl, eicosyl, icosyl, behenyl, docosyl, tetracosyl. alkenyl May be selected from the group consisting of nonenyl, undecenyl, dodecenyl, tridecylene, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, Octadecenyl, nindecene, eicosyl, hexadecenyl, docosyl, behenyl, and tetracosyl. Examples of preferred primary guanamines are shown in Table 1. 105083.doc 1316956
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常用名 银 雄雄 ffi a ^ ^ ^ ^ 霤齧 ox? tCj ns? ης e? op >q isil 绔 1荜1 缕筚龙 s 萆安咢 ：si 泠 i 埤 iim：i 藥砀安 竭：於安：令 螂碼 ；S 承：f 承 ：g 承 ：t 洽洽 洽朶 4 化學結構 丑 运 ώ1玲 1 1 1菩 Ills 5 5 1¾¾¾¾¾¾ 1 5 1 1 1 1 1 1 1 1 ξ 5 ΙϊΐϊΐίΐΙΐΙϊϊ ^¾¾¾¾¾¾¾¾¾¾¾ SShm^hhMhSSShKhhmh υδδδδδδυοοοο 化學名 十八碳烯基十六烧酿胺 十八炫基十八炫藥胺 十八碳烯基十八炫酿胺 十八絲十八猶_ 十/V碳稀基十/ν破稀酿胺 十/Υ烧基二十二^醒胺 十八碳稀基二十二^#酿胺 二十二*辨基十八炫酿胺 二十二^基十八碳烯酿胺 二十二基二十二^^酿胺 二十四炫基十二烧酿胺 二十四炫基十八貌酿胺 ¢21 十五炫基 十七炫基 十七炫基 十七破^基 十七破稀基 二 Η~^^^1#基 二 Η石基 十七炫基 十七破稀基 二十一碳烯基 十一炫基 十七炫基 P? 十八破煉基 十八炫基 十八碳稀基 十八统基 十八碳婦基 十八炫基 十八碳缲基 二十二^基 二十二基 二十二基 二十四烧基 二十四炫基 R2*炭原子數 v〇 卜卜卜 C*-» «―^ >·—< 卜卜1—|»^卜 1-^ fsj »-H ^ 艮碳原子數 ooooooooooooo〇(NrscN 寸寸 '^^^(NCNCNCNCN 1316956 二級醯胺之量可佔粉末金屬組合物之〇.〇5_2.0重量％， 較佳0.〇5-1.〇重量％。 本發明一具體實施例關於一種粉末金屬組合物，除至少 一種二級醯胺外，該組合物包括尚進一步含至少一種一級 酿胺之潤滑劑及/或黏著劑。該至少一種一級醯胺較佳為 具有12-24個碳原子之飽和或不飽和脂肪酸醯胺，較佳ι4_ 22個碳原子，最佳16-22個碳原子。 尤其較佳一級醯胺為硬脂酸醯胺（硬脂醯胺）、山蓊酸醯 胺（山蓊醯胺）、芥酸（芥醯胺）、棕櫚酸醯胺（椋櫚醯胺）及花 生酸醯胺（花生醯胺）。 根據本發明之一級和二級醯胺可以購得，或可用此項技 藝上已知之方法自購得的原料製造。 一級和二級醯胺之量可總共占粉末金屬組合物〇 〇5_2 〇 重量％，較佳0.05-1.0重量％。 對於包含兩種醯胺之本發明之具體實施例，至少一種一 級醯胺之量可為〇.〇5-1_〇重量％，至少一種二級醯胺之量可 為 0.05-1.0重量 ％。 潤滑劑及/或黏著劑可以各醯胺之固體顆粒形式加入粉 末金屬組合物。平均顆粒大小可以變化，但較佳小於15 〇 微米。 或者，潤滑劑及/或黏著劑可作為醯胺之熔融及隨後固 化顆粒狀混合物加入粉末金屬組合物。這可藉由以預定比 混合醯fe而達到’然後將混合物炫融，冷卻，且隨後研磨 成潤滑劑粉末。 105083.doc 1316956 可用根據本發明之至少一種二級醯胺作為黏著劑獲得黏 著混β物其中使選用的合金元素及至少一種二級醯胺黏 著到以鐵為主粉末。這可藉由混合以鐵為主之粉末與至少 一種根據本發明之二級醯胺，並將混合物加熱到高於至少 一種二級醯胺之熔點之溫度而達到。可進一步將至少一種 一級醯胺混入上述混合物，而加熱溫度然後可低於一級醯 胺之熔點。 除以上揭示的潤滑劑及/或黏著劑外，如需要，根據本 發明之粉末金屬組合物可包含其他潤滑劑，如硬脂酸辞、 硬脂酸鋰、EBS等。 為完成根據本發明之粉末金屬組合物之黏著，可使用其 他類型黏著系統，如醇酸樹脂、纖維素酯樹脂、在烷基中 具有1-4個破原子之經院基纖維素樹脂或熱塑性盼搭樹 脂。 如說明及附加請求項中所用，"以鐵為主之"粉末包括基 本由純鐵、已與其他元素預合金化以改良強度、硬二 質、電磁性質或最終產物其他理想性質之鐵粉末及與此等 合金元素之顆粒混合的鐵之顆粒（擴散退火混合物或純機 械混合物)所組成。合金元素之實例為銅、翻、鉻、錳、 麟、石墨態碳、鎳、石夕、棚、叙、敛、銘、姑及鶴，此等 疋素可單獨或組合使用，例如，以化合物形式㈣ρ和 FeMo)使用。 ㈣為U粉末可用於製備軟磁性零件’謂此應用可 電絕緣。粉末顆粒電絕緣體可由—種無機物質組成。美國 105083.doc •10- 1316956 專利第6348265號中揭示的絕緣類型尤其適用，該專利關 於一種基礎粉末之顆粒，此顆粒由具有絕緣含氧和鱗障壁 之基本純鐵所組成。絕緣粉末顆粒可作為s〇mal〇yTM 5〇0 和550自瑞典，豪格納斯AB公司（H〇ganas AB, Sweden)獲 得。 除以鐵為主之粉末和潤滑劑及/或黏著劑外，根據本發 明之粉末金屬組合物可含一或多種選自由處理助劑和硬相 所組成之群組之添加劑。Commonly used name silver male and male ffi a ^ ^ ^ ^ stalk ox? tCj ns? ης e? op >q isil 绔1荜1 缕筚龙 s 萆安咢:si 泠i 埤iim:i 药砀: Yu An: Ling weight; S Cheng: f Cheng: g Cheng: t Qiaqia Qiadu 4 Chemical structure ugly ώ 1 Ling 1 1 1 菩 Ills 5 5 13⁄43⁄43⁄43⁄43⁄43⁄4 1 5 1 1 1 1 1 1 1 ξ 5 ΙϊΐϊΐίΐΙΐΙϊϊ ^ 3⁄43⁄43⁄43⁄43⁄43⁄43⁄43⁄43⁄43⁄43⁄4 SShm^hhMhSSShKhhmh υδδδδδδυοοοο Chemical name octadecyl hexadecane octagonal amine 18 octagonal 18 octagonal medicinal amine octadecyl 18 octagonal amine 18 octa 18 _ 10/V carbon thin base /ν破稀牛胺十/Υ烧基二十二^ 醒amine 18 carbon dilute twenty two ^# 牛胺二十二二分基十八炫炫胺胺二二基基十八碳烯Amine Twenty-two Twenty-two Twenty-two ^^-enamined Twenty-four Hyun-based Twelve Burning Amines Twenty-four Hyun Eighteen Appearing Amines ¢21 Fifteen Hyun Seventeen Hyunji Seventeen Hyunki Seventeen Broken基七破稀基二Η~^^^1#基二Η石基17炫基七破稀基二十一碳烯十一十一炫基七炫基 P? Eight dazzling base eighteen carbon thin base eighteen Base eighteen carbon women's base eighteen radix eighteen carbon fluorenyl twenty two two base twenty two base twenty two twenty four burnt base twenty four radix R2 * carbon atom number v 〇 Bu Bu C * -» «―^ >·—< Bu Bu 1—|»^卜 1-^ fsj »-H ^ 艮Core number ooooooooooooo〇(NrscN inch inch '^^^(NCNCNCNCN 1316956 The amount of secondary guanamine can be粉末5_2.0% by weight, preferably 〇5-1.〇% by weight of the powder metal composition. One embodiment of the invention relates to a powder metal composition, in addition to at least one secondary guanamine The composition comprises a lubricant and/or an adhesive further comprising at least one primary amine. The at least one primary guanamine is preferably a saturated or unsaturated fatty acid decylamine having from 12 to 24 carbon atoms, preferably ι 4 22 One carbon atom, preferably 16-22 carbon atoms. Particularly preferred primary amine is decyl stearate (stearylamine), decyl behenate (ammonium), erucic acid (mucilamide) ), palmitate and palm amide (arachidamine). According to the invention, the primary and secondary guanamines are commercially available or can be used. The method known in the art is manufactured from commercially available raw materials. The amount of primary and secondary guanamine may be 〇〇5-2 〇% by weight, preferably 0.05-1.0% by weight, based on the powder metal composition. In a specific embodiment of the invention, the amount of at least one primary guanamine may be 〇.〇5-1_〇% by weight, and the amount of at least one secondary guanamine may be from 0.05 to 1.0% by weight. The lubricant and/or the adhesive may be added to the powder metal composition in the form of solid particles of each guanamine. The average particle size can vary, but is preferably less than 15 微米 microns. Alternatively, the lubricant and/or adhesive can be added to the powder metal composition as a melt of the guanamine and subsequent solidification of the particulate mixture. This can be achieved by mixing 醯fe at a predetermined ratio and then smearing the mixture, cooling, and then grinding into a lubricant powder. 105083.doc 1316956 Adhesive β can be obtained by using at least one secondary guanamine according to the present invention as an adhesive, wherein the selected alloying element and at least one secondary guanamine are adhered to an iron-based powder. This can be achieved by mixing an iron-based powder with at least one secondary guanamine according to the invention and heating the mixture to a temperature above the melting point of at least one of the secondary guanamines. Further, at least one primary guanamine may be further mixed into the above mixture, and the heating temperature may then be lower than the melting point of the primary guanamine. In addition to the lubricants and/or adhesives disclosed above, the powder metal composition according to the present invention may contain other lubricants such as stearic acid, lithium stearate, EBS, etc., if desired. In order to accomplish the adhesion of the powder metal composition according to the present invention, other types of adhesive systems such as alkyd resins, cellulose ester resins, trans-base cellulose resins having 1-4 broken atoms in the alkyl group, or thermoplastics may be used. Take the resin. As used in the description and in the appended claims, "iron-based" powders include iron that is essentially pure iron, pre-alloyed with other elements to improve strength, hardness, electromagnetic properties, or other desirable properties of the final product. A powder and iron particles (diffusion annealing mixture or pure mechanical mixture) mixed with particles of such alloying elements. Examples of alloying elements are copper, tumbling, chromium, manganese, lin, graphitic carbon, nickel, shi shi, shed, sui, shui, ming, gu and crane, which can be used alone or in combination, for example, as a compound Form (iv) ρ and FeMo) are used. (d) U powder can be used to prepare soft magnetic parts. This application can be electrically insulated. The powder particle electrical insulator may be composed of an inorganic substance. In particular, the type of insulation disclosed in U.S. Patent No. 1,034, 526, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety in its entirety in the in the in the Insulating powder granules are available as s〇mal〇yTM 5〇0 and 550 from Sweden, H〇ganas AB, Sweden. In addition to iron-based powders and lubricants and/or adhesives, the powder metal composition according to the present invention may contain one or more additives selected from the group consisting of processing aids and hard phases.
粉末金屬組合物中所用的處理助劑可由滑石、鎂橄欖 石、硫化錳、硫、二硫化鉬、氮化硼、碲、硒、二敗化鎖 及二氟化鈣所組成，且此等可單獨或組合使用。 粉末金屬組合物中所用硬相可由鎢之碳化物、釩、鉬、 鉻、Al2〇3、和各種陶瓷材料所組成。 本發明進一步關於一種製造坯體之方法，該方法包括， 將根據本發明之粉末金屬組合物緊壓成一種緊壓體，其中 該組合物包括一種為鐵為主之粉末和含至少一種具有通式The processing aid used in the powder metal composition may be composed of talc, forsterite, manganese sulfide, sulfur, molybdenum disulfide, boron nitride, antimony, selenium, disodium lock and calcium difluoride, and the like Used alone or in combination. The hard phase used in the powder metal composition can be composed of tungsten carbide, vanadium, molybdenum, chromium, Al2, 3, and various ceramic materials. The invention further relates to a method of making a blank, the method comprising compacting a powder metal composition according to the invention into a compact, wherein the composition comprises an iron-based powder and at least one formula
RkNH-CO-R2之二級醯胺之潤滑劑及/或黏著劑，其中心和 R2為相同或不同、直或分古 刀支、飽和或不飽和脂族烴基。姑 緊壓的坯體可經燒結或熱處理。 利用習知技術’可在緊壓步驟前將為鐵為主之粉末1 滑劑及/或黏著劑以及選用的添加劑混合成實㈣勻 組合物。 ’ 可在緊壓4預熱粉末金屬組合物及/或模。 本發明進一步關於至少— 種如上界定的 --級蕴胺作為潤 105083.doc -11 - 1316956 • 滑劑及/或黏著劑用於鐵或以鐵為主之粉末之用途。 本發明之另一具體實施例關於至少一種如上界定的二級 醯胺作為模壁潤滑劑之用途。 • 現在進一步用以下非限制實例描述本發明。 . 實例 在以下實例中使用具有表2中所揭示式之潤滑劑。 表2 化學名 結構式* 醯胺類型 對照：伸乙基雙硬脂醯胺 (EBS) CH3(CH2)16CONH(CH2)2NHCO(CH2)16CH3 雙醯胺 硬脂醯胺(S) ch3(ch2)16conh2 一級酿胺 花生醯胺(A) ch3(ch2)18conh2 一級醢胺 齐醯胺(E) CH3(CH2)7CH=CH(CH2)uCONH2 —級醯胺 山茶醯胺(B) ch3(ch2)20conh2 一級醢胺 硬脂基硬脂醯胺(SS) R1=C18:0 R2=C17:0 二級醯胺 芥基硬脂醯胺(ES) R1=C22:1 R2=C17:0 二級酿胺 油基棕櫚醯胺(OFj R 尸 C18:l R2=C15:0 二級酿胺 硬脂基芥醯胺(SE) Ri=C18:0 R2=C21:1 二級醯胺 油基硬脂醯胺(0S) Ri=C18:1 R2=C17:0 二級酿胺 硬脂基油醢胺(SO) Ri=C18:0 R2=C17:1 二級酿胺 二級醯胺的結構式指如前所述的Ri_nh-co-r2。 實例1 本實例說明在以鐵為主粉末混合物中作為粉末加入的不 同二級酿胺和不同二級和一級醯胺組合之潤滑性質。 將基礎粉末ASC 100.29(自瑞典，豪格納斯AB購得）與0.5 重量0/〇之石墨（uf·4，自克洛姆公司（Kropfmuhl))和0.8重 量之根據表3和4之潤滑劑在羅迪格（L0dige)混合機中混 合2分鐘。伸乙基雙硬脂醯胺（EBS，自德國，克萊瑞恩公 司（Clariant，Germany)作為Lic〇wax tm獲得）用作對照。潤 滑劑具有小於1 50微米之顆粒大小。包括二級和一級醯胺 105083.doc • 12· 1316956 二者之組合物包含50%各醯胺（全部組合物之〇8重量％)。 為制㈣性質，將具有45㈣内徑、55毫米外徑及ι〇 毫米高之環在環境溫度於三種不同緊壓壓力（彻、6〇〇和 800兆帕）緊壓4經緊壓零件脫模期間記錄脫模力。在脫 模後檢測零件之㈣密度，並計算樣品自模脫模所需的總 脫模能量/包封面積。所得脫模能量和密度顯示於表3和4 中。用根據本發明之粉末金屬组合物取得的較低脫模能量 與使用含EB S之對照組合物形成比較。RkNH-CO-R2 is a secondary guanamine lubricant and/or adhesive having a center or R2 which is the same or different, straight or divided knife, saturated or unsaturated aliphatic hydrocarbon group. The compacted body can be sintered or heat treated. The iron-based powder 1 slip and/or adhesive and optional additives can be mixed into a solid (tetra) homogenous composition prior to the compacting step using conventional techniques. The powder metal composition and/or mold may be preheated at a pressure of 4. The invention further relates to at least one of the above-defined levels of amines as Run 105083.doc -11 - 1316956 • The use of slip agents and/or adhesives for iron or iron-based powders. Another embodiment of the invention relates to the use of at least one secondary guanamine as defined above as a mold wall lubricant. • The invention will now be further described by the following non-limiting examples. EXAMPLES Lubricants having the formula disclosed in Table 2 were used in the following examples. Table 2 Chemical name structure formula * Indole type control: Ethyl distearylamine (EBS) CH3 (CH2) 16CONH (CH2) 2 NHCO (CH2) 16CH3 Diamide amine stearylamine (S) ch3 (ch2) 16conh2 primary amine amine peanut amide (A) ch3(ch2)18conh2 first-grade decylamine (E) CH3(CH2)7CH=CH(CH2)uCONH2-grade guanamine saponin (B) ch3(ch2)20conh2 Primary guanamine stearyl stearylamine (SS) R1=C18:0 R2=C17:0 Secondary guanamine mustard stearylamine (ES) R1=C22:1 R2=C17:0 Secondary amine Oil based palm amide (OFj R corpse C18: l R2 = C15: 0 secondary amine stearyl melamine (SE) Ri = C18: 0 R2 = C21:1 secondary guanamine oil based stearylamine (0S) Ri=C18:1 R2=C17:0 secondary amine amine stearyl amide (SO) Ri=C18:0 R2=C17:1 The structural formula of secondary amine amine guanamine refers to the former Said Ri_nh-co-r2. Example 1 This example illustrates the lubricating properties of different secondary amines and different secondary and primary guanamine combinations added as a powder in an iron-based powder mixture. The base powder ASC 100.29 ( From Sweden, Hauglas AB purchased) with 0.5 weight 0 / 〇 graphite (uf · 4, from Kropfmuhl) and 0.8 weight The amount of lubricant according to Tables 3 and 4 was mixed in a L0dige mixer for 2 minutes. Ethyl distearylamine (EBS, from Germany, Clariant, Germany as Lic 〇wax tm obtained) used as a control. Lubricants have a particle size of less than 150 microns. Both secondary and primary guanamines 105083.doc • 12·1316956 The composition of both contains 50% of the respective guanamines (all compositions) 〇8wt%). For the nature of (4), the ring with 45 (four) inner diameter, 55 mm outer diameter and ι mm high is pressed at three different pressing pressures (all, 6 〇〇 and 800 MPa) at ambient temperature. 4 Record the release force during the demolding of the pressed parts. Detect the (4) density of the part after demolding, and calculate the total release energy/encapsulation area required for the mold release from the mold. The resulting release energy and density are shown in In Tables 3 and 4, the lower release energy obtained with the powder metal composition according to the present invention was compared to the use of the control composition containing EB S.
潤滑劑 預混 _ 坯焦 【密度(克/釐米1 脫模能量（焦耳/夷 400兆帕 600兆帕 800兆帕 400兆帕 600兆帕 800兆帕 EBS(對照） 6.70 7.04 7.17 19.2 26.1 28.2 SS 6.72 7.06 7.19 17.6 24.7 ?7 Q ES 6.78 7.12 7.23 16.3 20.3 20 8 OP 6.78 7.14 7.25 16.7 21.3 20.3 SE 6.78 Γ 7.13 7.24 16.8 21.9 21 8 OS 6.78 7.13 7.24 17.7 21.3 20.5 so 6.79 7.13 7.23 15.9 21.4 20 4 表4.密方 1和脫模能量（二級+ 一級醯胺1 : H σ對照） 潤滑劑 --- 預混 1密度(克/釐米7i 脫模能量(焦耳/3 nF) 400兆帕 600兆帕 800¾ 帕 400兆帕 600兆帕 800兆帕 EBS(對照） 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.69 7.06 7.21 19.1 24.2 23.6 0P+S 6.70 7.06 7.19 18.2 22.1 22.3 ES+S 6.71 7.06 7.19 17.9 21.5 21.8 ES+E 6.72 7.11 7.23 17.8 20.7 19.0 實例2 將基礎粉末ASC 100.29與2重量％之銅（-100微米）、〇·8重 量％之石墨及0.8重量之潤滑劑（a) EBS或b)油基棕橺醯胺） 在羅迪格混合機中混合2分鐘。潤滑劑具有小於150微米之 105083.doc -13- 1316956 顆粒大小。為檢測元件燒結後生成錄斑，將具有㈠毫米直 徑及32毫米高之圓柱形元件在環境温度緊㈣7」克/釐米3 之述體密度。一個圓枉之番县 重量為700克。將元件在1120°c 於含90/1 〇 N2/H2之惫裔德 亂巩燒、，，〇 1 5分鐘。元件相片顯示於圖 ⑷伸乙基雙硬脂酿胺（EBS>lb)油基標搁醯胺中，其中圖 U)顯示生成鏽斑，與其相比，自根據本發明之粉末組合 物產生之零件lb)沒有鏽斑。 實例3 本實例說明在與以鐵為主之粉末混合物混合前一起熔 融、冷卻及研磨的不同二級和一級醯胺之組合之潤滑性 質。 根據以下方法產生潤滑劑組合物：將經混合的潤滑劑 (50%—級和二級醯胺）在8〇-11〇一起熔融，然後冷卻。 然後將該材料研磨到低於15 0微米之平均顆粒大小。 將基礎粉末ASC 100.29與0.5重量％之石墨及〇.8重量之 潤滑劑組合（見表5)在羅迪格混合機中混合2分鐘。為檢測 潤滑性質’將具有45毫米内徑、55毫米外徑及1〇毫米高之 環在環境溫度於三種不同緊墨壓力（400、600和800兆帕）緊 壓。所得脫模能量和密度顯示於表5中。 表5.密度和脫模能量（二級+—級醯胺和對照） 潤滑劑 經熔融及固化 坯截 【密度(克/愛米） 脫模能量(焦耳/釐米^ 400兆帕 600死帕 800兆^帕 400兆帕 600兆帕 800兆帕 EBS(對照） 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.70 7.06 7.20 18.8 22.4 22.6 OP+S 6.71 7.07 7.20 18.5 23.2 24.4 ES+S 6.71 7.07 7.20 18.9 22.7 23.5 ES+E 6.70 7.07 7.20 17.2 19.8 18.0 105083.doc -14- 1316956 比較表5中的試驗結果可以看到，與自已知潤滑劑EB s 製造之樣品比較，自根據本發明之粉末金屬組合物產生的 樣品顯示較低脫模能量。 實例4 本實例說明在粉末金屬混合物中不同醯胺組合之潤滑及 黏著性質。Lubricant premix _ billet coke [density (g / cm 1 release energy (Joule / Yi 400 MPa 600 MPa 800 MPa 400 MPa 600 MPa 800 MPa EBS (control) 6.70 7.04 7.17 19.2 26.1 28.2 SS 6.72 7.06 7.19 17.6 24.7 ?7 Q ES 6.78 7.12 7.23 16.3 20.3 20 8 OP 6.78 7.14 7.25 16.7 21.3 20.3 SE 6.78 Γ 7.13 7.24 16.8 21.9 21 8 OS 6.78 7.13 7.24 17.7 21.3 20.5 so 6.79 7.13 7.23 15.9 21.4 20 4 Table 4. Compact 1 and release energy (secondary + primary guanamine 1: H σ control) Lubricant --- premix 1 density (g / cm 7i release energy (joule / 3 nF) 400 MPa 600 MPa 8003⁄4 PA 400 MPa 600 MPa 800 MPa EBS (control) 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.69 7.06 7.21 19.1 24.2 23.6 0P+S 6.70 7.06 7.19 18.2 22.1 22.3 ES+S 6.71 7.06 7.19 17.9 21.5 21.8 ES+E 6.72 7.11 7.23 17.8 20.7 19.0 Example 2 Base powder ASC 100.29 with 2% by weight of copper (-100 μm), 〇·8 wt% of graphite and 0.8 wt% of lubricant (a) EBS or b) oil-based palm Amine) Mix for 2 minutes in a Rodigue mixer. Lubricant has a small 150 micron 105083.doc -13- 1316956 Particle size. For the recording element to form a spot after sintering, the cylindrical element having a diameter of (a) mm and a height of 32 mm is tight at ambient temperature (4) 7" g/cm3. The weight of a round 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县The bis-stearyl amine (EBS > lb) oil-based ammine, wherein Figure U) shows the formation of rust, compared to the lb) of the part lb) produced from the powder composition according to the invention. EXAMPLE 3 This example illustrates the lubricity of a combination of different secondary and primary guanamines that are melted, cooled, and ground prior to mixing with an iron-based powder mixture. The lubricant composition was produced according to the following method: The mixed lubricant (50%-grade and secondary guanamine) was melted together at 8 〇-11 Torr and then cooled. The material is then ground to an average particle size below 150 microns. The base powder ASC 100.29 was combined with 0.5% by weight of graphite and 〇.8 by weight of lubricant (see Table 5) for 2 minutes in a Rodigue mixer. To test the lubricity properties, a ring with a 45 mm inner diameter, 55 mm outer diameter and 1 mm high height was pressed at ambient temperature at three different tight ink pressures (400, 600 and 800 MPa). The resulting release energy and density are shown in Table 5. Table 5. Density and demolding energy (secondary + grade guanamine and control) Lubricant melted and solidified cut [density (g / ami) release energy (joule / cm ^ 400 MPa 600 dead par 800 Mega ^ 400 400 MPa 600 MPa 800 MPa EBS (control) 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.70 7.06 7.20 18.8 22.4 22.6 OP+S 6.71 7.07 7.20 18.5 23.2 24.4 ES+S 6.71 7.07 7.20 18.9 22.7 23.5 ES +E 6.70 7.07 7.20 17.2 19.8 18.0 105083.doc -14- 1316956 Comparing the test results in Table 5, it can be seen that the sample produced from the powder metal composition according to the present invention is compared with the sample produced from the known lubricant EB s. Shows lower mold release energy.Example 4 This example illustrates the lubrication and adhesion properties of different guanamine combinations in a powder metal mixture.
潤滑劑具有小於150微米之顆粒大小。將基礎粉末ASC 100.29與2重量％之(^-1〇〇、08重量％之石墨及〇8重量之 根據表6之潤滑劑組合物在羅迪格混合機中混合2分鐘。將 具有EBS之混合物作為對照保持，同時，在另一混合機中 犯&期間，將含醯胺之混合物加熱到高於二級之熔點但低 於-級酿胺之溶融之溫度，隨後冷卻以完成添加劑對鐵粉 末之黏著。潤滑劑之熔融溫度揭示於表7中。 此外，對在環境溫度於三種不同緊壓壓力（400、600和 800死帕）緊壓的具有55毫米外程、45毫米内徑及1〇毫米高 之環檢測脫模能量。所得脫模能量和3$體密度顯示於表8 中。 r-- ^ 組合 一机離妝 0.2重量％ 二級醯胺 0.6重量％ ES "^ B Q 〇P~~~~~- OP -- B EBS(對照1) (0.8重量％) 105083.doc -15· 1316956 表7·潤滑劑之熔融溫度 潤滑劑 熔融溫度(°c) ES 72.9 ΟΡ 66.9 Β 101.9 S 106.6 表8.密度和脫模能量(一級+二級酿胺和對照） 潤滑劑 熔融黏著 坯體密度(克/釐米3) 脫模能量(焦耳/釐米） 400死帕 600兆帕 800祀帕 400兆帕 600死帕 800兆帕 ES+B 6.75 7.06 7.19 18.5 24.6 28.1 OP+S 6.73 7.09 7.18 19.3 26.6 1 28.3 OP+B 6.77 7.08 7.19 19.9 25.3 27.1 EBS(對照） 6.74 7.06 7.17 21.4 30.8 32.8The lubricant has a particle size of less than 150 microns. The base powder ASC 100.29 was mixed with 2% by weight of (^-1 〇〇, 08% by weight of graphite and 〇8 by weight of the lubricant composition according to Table 6 in a Rodigue mixer for 2 minutes. The mixture is maintained as a control while the mixture containing the decylamine is heated to a temperature above the melting point of the second stage but below the melting point of the -ther amine during the time of & in another mixer, followed by cooling to complete the additive pair Adhesion of iron powder. The melting temperature of the lubricant is disclosed in Table 7. In addition, it has a 55 mm outer diameter and a 45 mm inner diameter for compacting at three different pressing pressures (400, 600 and 800 dead) at ambient temperature. And the 1 mm high ring was used to detect the release energy. The obtained release energy and 3$ bulk density are shown in Table 8. r-- ^ Combined machine dismantling 0.2% by weight II decyl 0.6% by weight ES "^ BQ 〇P~~~~~- OP -- B EBS (Control 1) (0.8% by weight) 105083.doc -15· 1316956 Table 7·Lubricating temperature of lubricant Melting temperature of lubricant (°c) ES 72.9 ΟΡ 66.9 Β 101.9 S 106.6 Table 8. Density and release energy (primary + secondary amine and control) lubricant Melt density of the body (g/cm3) Demoulding energy (Joules/cm) 400 dead par 600 MPa 800 祀 400 400 MPa 600 dead par 800 MPa ES+B 6.75 7.06 7.19 18.5 24.6 28.1 OP+S 6.73 7.09 7.18 19.3 26.6 1 28.3 OP+B 6.77 7.08 7.19 19.9 25.3 27.1 EBS (control) 6.74 7.06 7.17 21.4 30.8 32.8
與用作對照的潤滑劑（即，EBS)製造之樣品比較，用根 據本發明之潤滑劑製造之樣品顯示較低脫模能量。利用含 根據本發明之潤滑劑之粉末組合物產生具有優良表面光潔 度之緊壓燒結零件（在112〇。(：於90/10 Ν2/Η2中燒結30分 鐘），即，基本無劃痕及鏽斑生成。 實例5 將其中顆粒由無機絕緣物包圍的粗糙軟磁性以鐵為主之 粉末與根據表9之二級醯胺潤滑劑混合。用已知物質硬脂 I鋅及EBS作為對照潤滑劑。所用以鐵為主之粉末之顆粒 大小分佈揭示於表1 〇中。 將所得混合物轉移到模，並在1100兆帕之緊壓壓力以單 °擠壓移動緊壓成具有25毫米直徑之圓柱形試樣(5〇 間）,\所用模材料為習知工具鋼。在經緊壓樣品脫模期 脫楱力。计算樣品自模脫模所需的總脫模能量/ 105083.doc -16、 1316956 包封面積。 關於生態之脫模能量、坯體密度及表面外觀之檢測結果 顯示於表9中。利用根據本發明之粉末組合物產生之結果 為，與對照組合物比較，獲得具有優良表面外觀及低脫模 能量之緊壓元件。 表9.密度、脫模能量及表面外觀 混合物 編號 潤滑劑 (0.2重量％) 脫模能量 (焦耳/釐米2) 述體密度 (克/爱米3) 表面外觀 1 ES 76 7.65 極佳 2 SE 71 7.66 極佳 3 SS 78 7.63 極佳 4 OP 76 7.66 極佳 對照1 硬脂酸鋅 117 7.66 不可接受 對照2 EBS 113 7.64 極佳 表10 顆粒大小(微米） 粗粉末(重量％) >425 0.1 425-212 64.2 212-150 34.1 150-106 1.1 106-75 0.3 45-75 0.2 <45 0 【圖式簡單說明】 圖1顯示在燒結後由於使用不同潤滑劑之元件之鏽斑生 成。 la) 伸乙基雙硬脂醢胺（EBS); lb) 油基棕櫚醯胺（根據本發明之二級醯胺）。 105083.doc -17-Samples made with the lubricant according to the present invention showed lower demolding energy as compared to samples made with the lubricant used as a control (i.e., EBS). Using a powder composition containing a lubricant according to the present invention to produce a compacted sintered part having an excellent surface finish (at 112 Å. (: sintered in 90/10 Ν 2 / Η 2 for 30 minutes), that is, substantially free from scratches and rust spots Example 5 A rough soft magnetic iron-based powder in which the particles were surrounded by an inorganic insulator was mixed with a secondary guanamine lubricant according to Table 9. The known materials were stearic acid I zinc and EBS as a control lubricant. The particle size distribution of the iron-based powder is disclosed in Table 1. The resulting mixture was transferred to a mold and pressed into a cylindrical shape having a diameter of 25 mm by a single pressing operation at a pressing pressure of 1100 MPa. For the sample (5〇), the mold material used is the conventional tool steel. The release force is released during the demolding period of the pressed sample. Calculate the total release energy required for the sample to be demolded from the mold / 105083.doc -16, 1316956 Encapsulation area. The results of the detection of ecological release energy, green body density and surface appearance are shown in Table 9. As a result of using the powder composition according to the present invention, an excellent surface was obtained as compared with the control composition. Appearance and Release element for demolding energy. Table 9. Density, release energy and surface appearance. Mixture number lubricant (0.2% by weight) Release energy (Joules/cm2) Descriptor density (g/Ami 3) Surface appearance 1 ES 76 7.65 Excellent 2 SE 71 7.66 Excellent 3 SS 78 7.63 Excellent 4 OP 76 7.66 Excellent Control 1 Zinc Stearate 117 7.66 Unacceptable Control 2 EBS 113 7.64 Excellent Table 10 Particle Size (μm) Coarse Powder ( % by weight) >425 0.1 425-212 64.2 212-150 34.1 150-106 1.1 106-75 0.3 45-75 0.2 <45 0 [Simple description of the drawing] Figure 1 shows the components due to the use of different lubricants after sintering The rust is formed. la) Ethyl bis stearylamine (EBS); lb) oleyl palm amide (second decylamine according to the invention). 105083.doc -17-