CN1902332A - 包括微粉化淀粉的粉末金属混合物 - Google Patents
包括微粉化淀粉的粉末金属混合物 Download PDFInfo
- Publication number
- CN1902332A CN1902332A CNA2004800403539A CN200480040353A CN1902332A CN 1902332 A CN1902332 A CN 1902332A CN A2004800403539 A CNA2004800403539 A CN A2004800403539A CN 200480040353 A CN200480040353 A CN 200480040353A CN 1902332 A CN1902332 A CN 1902332A
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- China
- Prior art keywords
- lubricant
- mixture
- starch
- less
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
本发明提供一种粉末金属混合物,其包含常规上用于与改良润滑剂组合来生产粉末金属配件的润滑剂粉末。通过向其添加一定量的小于平均金属颗粒的淀粉颗粒和微粉化纤维素纤维(视需要)来改良常规上用于压紧和烧结所选粉末金属混合物的润滑剂,其中所述量小到使得所述改良润滑剂以小于所述混合物重量计的2%的量存在。由所述淀粉或(淀粉+纤维)的改良润滑剂制得的粉末金属混合物的霍尔表观密度和霍尔流率保持在据认为适合生产压紧粉末金属配件的范围内。使用改良润滑剂来代替常规润滑剂提高了通过压紧所述混合物而制得的配件的生坯强度,并改良了尺寸一致性。
Description
对相关申请案的交叉参考:
本专利申请案是2002年8月28日申请的序列号第10/229,452号的部分接续申请案,而第10/229,452号是2001年5月21日申请的序列号第09/961,842号的部分接续申请案,第09/961,842号在2003年1月14号被颁布为美国专利第6,506,712号(“″712专利”)。
技术领域
本发明涉及一种新颖粉末金属混合物,其中一与粘合剂和润滑剂组合的颗粒铁金属粉末常规上被模制成一具有任意形状和尺寸且具有足够的生坯强度以从模具中脱模的物件,其中所述物件在不刻划模具并且不产生太多的热量而使得润滑剂在压紧配件上产生气泡的情况下被模制。
背景技术
自从发现粉末形状的适当磨碎的金属颗粒与也为磨碎形式的粘合剂和润滑剂混合的混合物能被压紧并烧结以生产具有任意形状和尺寸的物件以来,用于器具、车辆和机器的各种金属配件的大规模生产的需要已推动粉末冶金技术的发展。在这项技术中,“粉末金属混合物”指的是大量颗粒,其每一者在平均当量直径(average equivalentdiameter)上小于150μm(微米),其中优选地其最大尺寸(金属颗粒通常为最大)优选地具有小于75μm的平均当量直径,最小金属颗粒具有约25μm的平均当量直径,且非金属添加剂通常具有小于金属颗粒的平均当量直径、通常小于50μm的平均当量直径。根据经烧结或经烧结并热处理的铁物件的所要物理性质,添加一大批粉末添加剂。这些添加剂中最常用的是润滑剂和/或石墨,接下来是例如镍、铜、钼、锰、铬、钴的金属和/或例如硫化物、磷化物和其类似物的有机金属或金属化合物,其在被烧结和/或热处理时与粉末金属形成合金。
本发明中术语“粉末金属混合物”指的是铁金属颗粒的混合物,其中铁(Fe)的存在量大于90%,其余成分为添加剂,例如润滑剂、粘合剂(视需要而定,其可与所述润滑剂相同或不同)和合金成分(例如石墨和金属),其每一者的存在量少于以总混合物(包括粉末)重量计的2%(重量%)。
术语“润滑剂”指的是一种颗粒粉末,其尺寸不大于约100μm,且其平均当量直径通常在约5μm到25μm的范围内;在本发明中,润滑剂经改良以基本上由一与颗粒淀粉掺合的润滑剂粉末构成,其中所述润滑剂粉末为例如常规上用于制造压紧块粉末金属的润滑剂粉末,所述颗粒淀粉的平均当量直径小于150μm,优选地小于50μm,该润滑剂粉末视需要可与不多于相等量的微米级碎片纤维素纤维(如淀粉、多糖)组合,只要90%的碎片的长度小于金属颗粒的平均当量直径。为方便简洁起见,仅具有淀粉的常规上使用的粉末金属润滑剂的改良被称为“淀粉润滑剂”。
因为像淀粉颗粒这样的粉末金属颗粒的形状可能不规则,所以颗粒的当量直径指的是其被假设为一具有相等体积的球体时的直径。
可与淀粉颗粒混合的纤维素碎片优选地比50μm小得多且在一狭窄尺寸范围内,即至少90重量%在长度上小于10μm,且所有碎片的平均长度在约4到5μm的范围内。碎片被称为是被“微粉化的”,因为其是通过把长度小于约6.35mm(0.25″)的短纤维素纤维进料到一市售喷射式分级碾磨机或“微粉化器”(例如由Fluid EnergyAl-Jet公司制造的30型旋转喷射)来方便地获得的。最优选地,纤维素纤维(例如棉花、大麻、马尼拉麻、剑麻、黄麻和其类似物)首先由足量的辐射照射以改变其表面结构,优选地通过把纤维暴露到电子束照射中以接收一在相当于约30到100百万拉德(MegaRad)范围内的剂量(通常以千戈瑞(kGy)来测量),如在前述′712专利中详细描述,所述揭示内容如同在本文完全阐述那样以引用的方式并入本文中。因为,像淀粉颗粒一样,纤维素碎片没有明显的润滑性,所以其被一起称为“非润滑剂”。
实用粉末混合物最重要的标准是其均质性,如果没有均质性,压紧金属配件的成分中将具有不可接受的差异,不仅是配件与配件之间,而且是在一个配件自身内部。术语“配件”可与更正式的术语“物件”交换使用。此均质性不仅包含单位体积粉末的质量中颗粒的分布,而且包含粉末混合物的容积密度(被测量为“霍尔表观密度”)和流动特性(被测量为“霍尔流率”)。表观密度是单位体积的非压紧粉末的质量。按照ASTMB-212(“金属粉末和粉末冶金产品的标准测试方法”中的金属粉末工业协会“MPIF”测试方法04)中阐述来测量霍尔表观密度。流率被量化为一标准重量的粉末流经霍尔流量计所需的时间。霍尔流率由ASTM B-213(MPIF测试方法03)规定。容积密度和流动的差异将导致“填充”和压紧配件的尺寸的差异,其中所述“填充”是在混合物被压紧之前填入模槽中的粉末混合物的量。在较小程度上,缺少均质性反映在压紧配件(尤其是在模制配件的敏感部分(例如齿轮的齿)中)的生坯强度的差异。
主要因为充分生坯强度是通过增加压紧压力来获得的,所以生坯强度作为重要问题仅在以下情况中引起注意:其中压紧或模制压力已经高到明显地缩短模具的使用寿命,和/或当在不能预防压坯被碰撞(即使不是强有力地碰撞)的条件下被从模具中脱模或被自动输送到烧结炉时,被损坏的压紧配件的数目令人担忧。
生坯强度被测量为打破未经烧结的坯块(标准长方形棒)所要的压力,如在ASTMB-312(MPIF测试方法15)中阐述。
虽然术语“粘合剂”和“润滑剂”似乎用于在待压紧的粉末金属掺合物中专门执行不同功能,但实际上,相同功能可由单一成分执行,虽然与由不同高度专业化材料执行相比,每一功能可能达到更大或更小程度。确切地说,乙撑双硬脂酰胺(“EBS”)有时被称为“粘合剂”,虽然其还可用作为润滑剂;且金属皂和蜡通常被称为“润滑剂”,虽然其还可以用作粘合剂。术语“掺合物”指的是铁金属粉末,包括所有基本上被均质分散且适合被压紧的成分。“铁”金属粉末意指这样一种粉末,其中金属颗粒主要含有元素铁(Fe),通常至少75%的Fe。粘合剂将石墨和合金组份的颗粒粘合到金属颗粒的表面上。润滑剂降低了当粉末受到剪切或被压时所产生的摩擦力;因此,具有润滑剂颗粒的金属粉末比没有润滑剂的金属粉末更容易流动;并且,金属颗粒上添加有润滑剂的粉术混合物可在模具中在压力下被压紧,且如果坯块具有足够的生坯强度,那么其可在使得模具配件上具有更少磨损和撕裂的情况下从模具中脱模。
通常,接着烧结所述生物件。烧结棒的强度被测量为“横向断裂强度”(“TRS”),其使用一标准TRS夹具来测量,如ASTM B-528(MPIF测试方法41)中描述。如果所述TRS令人满意,那么抗张强度一般也令人满意。根据粉末金属和添加剂的混合物(物件自其模制)的成分和其最终用途,其可接受进一步加工工序,例如定型/冲制、再烧结、热处理和其他工序。
认识到金属、粘合剂和/或润滑剂的组份粉末和一种或一种以上额外添加剂在尺寸、密度和形状上不同,通过选择具有类似尺寸和形状的颗粒并在使用所述粉末混合物之前充分混合各种颗粒来将均质性问题最小化。在此机制中,显然任何关于把淀粉颗粒和植物性材料的有机纤维(视需要)一起与润滑剂和金属颗粒混合的想法被迅速驱除,无论所述非润滑剂在其他情况下是多么有利。
此外,至今为止,淀粉颗粒尚未被用作粉末金属配件中的润滑剂或粘合剂,因为像纤维素和其他多糖那样,不认为淀粉对此目的具有任何重要有利价值。虽然淀粉和棉花具有类似化学式,但纤维素是纤维二糖聚合物,而淀粉是多糖聚合物。每种聚合物在结构上不同,且结构上的这种差异导致性质极为不同。例如,淀粉一般可供人类食用,而纤维素不是。此外,聚纤维二糖天然地出现为纤维状,而淀粉是颗粒状。
如果混合物将用于压紧和烧结配件的大规模生产中,那么添加小到以总粉末混合物重量计的2%的量的淀粉颗粒,无论水溶性淀粉还是不溶于水的淀粉,且其平均直径不小于50μm(虽然与用于可压紧粉末混合物中的金属颗粒的平均当量直径在相同尺寸范围内),均会导致不可接受的容积或表观密度以及流动特征。含有50μm或更长的淀粉颗粒的粉末金属混合物的不良物理性质可归因于颗粒所占的体积和其个体形状的不规则性。添加总量小到2重量%(不管其各自比例如何)的视需要与微粉化棉纤维组合的小于50μm的淀粉颗粒(被称为“微粉化淀粉”)产生与单独添加淀粉相同的影响。
另一方面,将很好地认识到由粉末混合物中的较小颗粒提供的表面面积相对于由较大颗粒提供的面积的增加损害了粉末混合物的“流动性”或流动特征,从而导致需要一段更长时间来填充模具且造成压紧配件中非均质性的额外风险。虽然在实验室中压紧大约一打配件时此流动性并不成为问题,但在生产设备中所述问题可能是重要的,其中单位时间内可产生的配件数目是一个决定性因素。
另一个近年来已日益突出的严重问题是“粉化”程度(特别是石墨),以及在烧结过程中汽化硬脂酸锌的有害副作用,其中硬脂酸锌通常被用作润滑剂。为了解决后一个问题,特别需要清洁烧结炉和其烟道,随着包括蜡和金属皂的大量其他润滑剂的揭示此项技术正在激增。为了最小化或排除硬脂酸锌的使用,在美国专利第6,511,945号中揭示了与寡聚酰胺组合的聚环氧乙烷;且EBS或多羧酸酰胺蜡被用作粘合剂,但是制造均质粉末混合物通常需要加热蜡以使其作为一涂层均匀地分布在金属颗粒上,如分别在Storstrom等人的美国专利第5,480,469号和Vidarsson等人的美国专利第6,573,225号中揭示。为了改进润滑作用,美国专利第6,413,919号使用两种众所周知的润滑剂的组合,其中每一者凭借其自身能力是有效的,其中一种是脂肪酸单-或双-酰胺(例如EBS),另一种是金属皂(例如硬脂酸锌),并且依靠处理所述混合物来形成由一种润滑剂组成且涂覆有另一种润滑剂的核心。
发明内容
提供一具有任意形状和尺寸的物件,其由以下材料模制得到:(i)铁金属粉末,其平均颗粒尺寸小于约150μm(30筛目美国标准筛系列);(ii)颗粒状、可流动润滑剂,其平均颗粒尺寸小于约50μm、优选地小于30μm;和(iii)淀粉颗粒,其平均当量直径小于50μm、优选地在约1μm到50μm的范围内,或(iv)与微粉化纤维素纤维组合的淀粉颗粒;所述物件由粉末金属混合物模制得到,在所述混合物中润滑剂和淀粉颗粒可一起以一约0.01重量%到小于2重量%的范围内的量存在,每一者优选地以小于以混合物重量计的1%的量存在。约90重量%的淀粉颗粒的平均当量直径在5到50μm的范围内;5重量%到40重量%范围内的淀粉颗粒的平均当量直径在2到20μm的范围内,且1重量%到20重量%的淀粉颗粒的平均当量直径在1到10μm的范围内,如在Microtrac标准范围颗粒分析器(Microtrac Standard Range Particle Analyzer)中所测量得到。
最优选地是已由X射线或γ射线(优选地,γ射线)照射的前述尺寸范围内的淀粉颗粒,所述射线的强度足以提供一可至少有效改良淀粉颗粒的表面(即使不改良其化学结构)的剂量。有代表性的是玉米淀粉的颗粒,例如可从National Starch & Chemical公司购得的Purity21C,其已从钴60γ射线源接收约10到30百万拉德范围内、最优选地约15百万拉德的剂量。不同淀粉所需的剂量在很大程度上依赖于其在不受照射下的适用性而变化。一般而言,优选地为此特定目的照射所有淀粉颗粒,因为经照射的颗粒的物理化学性质与那些未经照射的颗粒具有出乎意料的不同。
由于依赖于蜡和/或金属皂的固有的众所周知的润滑性与已知球形的雾化润滑剂的组合来提供最高流率和表观密度(在前述′919专利中),因而特别料想不到淀粉颗粒(一种不具有明显润滑性且具有较低表观密度的材料)能与已知润滑剂组合且生产淀粉改良润滑剂,其不但基本上与不具有淀粉的润滑剂具有相同的物理性质,而且还产生了表观密度大体上类似的掺合物和生坯强度更好的坯块。
虽然在上文指定的尺寸范围和量中的淀粉颗粒自身不对粉末金属掺合物提供明显的润滑性,但其可与任何适于提供可压紧粉末金属混合物(无论低合金钢或不锈钢,还是预合金铁粉末)的润滑剂一起使用;优选地,调整纤维素纤维与润滑剂的比率以提供“改良润滑剂”或“淀粉润滑剂”,其与粉末金属掺合,为所选生配件产生掺合物,所述掺合物具有由模具的生产要求规定的霍尔表观密度和流率的规格。由淀粉润滑剂压紧形成的生配件提供比在相同条件下由相同润滑剂(与淀粉润滑剂存在量相同但不具有纤维)压紧形成的另一配件的生坯强度更高的生坯强度,且同时满足烧结配件的硬度和TRS的预定规格。“低合金”粉末意指基于铁的粉末,其可含有0.5重量%到5重量%的石墨和0.1%到25%的从由Ni、Cu、Cr、Mo、Mn、P、Si、V和W构成的组中选出的元素。“不锈钢”意指具有很多种成分但总是含有较高百分比的铬(约8%到约25%)、通常0到12%的Ni和O到约0.5%的C(碳)的抗腐蚀钢。“预合金”意指铁以使其与一种或一种以上合金元素大体上均质地互相混合的方式被熔化处理。低合金钢配件通常由比铬或镍少得多的量的其他元素制成,其中铜的使用量高于Mn、Mo、Si、V、P和W,高达5%,且Mn、Mo、Si、V、P和W的使用量通常小于约2%。
铁金属粉末可从前述任何基于铁的粉末中选出。通常,铁金属粉末为雾化粉末或从海绵铁中取得,其颗粒的尺寸范围经选择以满足烧结最终产品的规格。
虽然可使用任何常规上使用的蜡制润滑剂(例如EBS),但是一种优选润滑剂是市售为聚合低碳烯烃氧化物或氧化聚烯烃均聚物或共聚物的微粉化聚烯烃蜡,其中所述烯烃具有2到4个碳原子;最优选的是氧化微粉化聚烯烃均聚物蜡。由于少于0.1重量%的非润滑剂本身与润滑剂相比不具有明显优点,因此所使用的淀粉润滑剂或(淀粉润滑剂+纤维素碎片)的量优选地在0.25重量%到1重量%的范围内,且淀粉润滑剂中润滑剂/淀粉或润滑剂/(淀粉+纤维素碎片)的重量比在约1∶2到10∶1的范围内,优选地在1∶1到4∶1的范围内。
揭示一种用于制造均质粉末金属混合物的方法,其包含:将平均当量颗粒直径小于约150μm的金属颗粒与包括存在量小于以混合物重量计的2%的改良润滑剂和所属领域中常规上所使用的粘合剂、加工助剂和添加剂(视需要)混合一段充分时间以产生以下规格:(i)霍尔表观密度在数值上比由不具有淀粉颗粒的常规润滑剂制得的相同粉末金属混合物获得的霍尔表观密度小不小于10%;和(ii)霍尔流率为至少25-35sec/50g混合物,其中所述改良润滑剂基本上由优选地平均当量直径小于50μm的颗粒润滑剂和平均当量直径小于50μm的淀粉颗粒(其视需要与微粉化纤维素纤维组合)的组合构成。优选地,所述霍尔表观密度在数值上大于由不具有淀粉颗粒的常规润滑剂制得的相同粉末金属混合物获得的霍尔表观密度。
在由小于2重量%的常规润滑剂制得的粉末金属混合物(该混合物的霍尔流率低得无法接受,为小于25sec/50g)中,添加重量份相等但至少0.1重量%的颗粒淀粉或淀粉和微粉化纤维素纤维(其自身提供具有可忽视润滑性的混合物)(以便使得非润滑剂和润滑剂一起的存在量小于以混合物重量计的2%)将产生一种掺合物,其不仅具有所要的霍尔表观密度和流率,而且导致比省略淀粉颗粒时更高的生坯强度。不可接受的流率是导致不均匀填充模槽的流率。大多数粉末金属混合物的最佳填充在25到35sec/50g的范围内,如果生产速度的需要不是太高的话,可接受稍微更长的时间,通常多达40sec/50g。
一种商业上可用的铁粉末金属掺合物(其包括小于2重量%的改良润滑剂,所述改良润滑剂包括0.1重量%到小于1重量%的淀粉颗粒和0.1重量%到小于1重量%的常规且优选为聚合的润滑剂的组合)具有2.7到3.5g/cc范围内、优选地2.9到3.3g/cc范围内的霍尔表观密度和25到35sec/50g、优选地29到33sec/50g的霍尔流率。流动太慢或根本不流动的掺合物通常毫无困难地流过粉末箱的导管;例如一些淀粉重量比可能在填充模槽时遇到的此小困难可通过使用导管上的摇动构件(例如机械或声波振动器)来解决。通常由所述新颖改良润滑剂获得的略微较低的表观密度通过加深常规上和表观密度较高的掺合物一起使用的模槽来得到补偿。
与例如当量直径小于约50μm的聚烯烃蜡颗粒的微粉化人造蜡组合的如本文所定义的淀粉颗粒是一种新颖组成物的成分,发现所述新颖组成物不仅是例如硬脂酸锌的金属皂或脂肪酸单-或双-酰胺的替代物(全部或部分),而且提供比可由相等重量的不具有淀粉颗粒的润滑剂获得的生坯强度更高的生坯强度。当含有所述淀粉润滑剂的所模制的生铁粉末金属物件在常规烧结炉的无氧条件下被烧结时,不需要像烧结含硬脂酸锌的物件的情况那样频繁地清理炉的烟道。淀粉颗粒还可以与例如石墨的无机润滑剂组合,纤维的功能部分在于代替其他情况下所使用的石墨的一部分;或者与例如硬脂酸锌的金属有机化合物组合,纤维的功能部分在于代替其他情况下所使用的金属有机化合物的一部分。
附图说明
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具体实施方式
重要的是,使用前述尺寸范围内的淀粉颗粒,而相对不重要的是γ照射所述颗粒以改良其表面。术语“淀粉颗粒”指的是从天然存在的植物性物质中取得的淀粉的颗粒,所述植物性物质例如玉米、土豆、木薯、稻米、豌豆、小麦和其类似物,其产生前述尺寸范围内的颗粒。人们相信当10到30百万拉德范围内的剂量输送到大量淀粉颗粒时,其表面结构以促进粉末金属混合物在经照射的淀粉与常规有机润滑剂的同样小或更小的颗粒混合时的流动的方式得到改良。
淀粉优选地包含在纤维鼓中,其被输送到一辐射室中且被保持若干连续周期,直到获得所要剂量。剂量太低(例如在例如通常用于杀菌的2到6百万拉德的范围内),不利地影响其中使用经照射的淀粉颗粒的粉末金属混合物的最理想表观密度和流率;剂量太高可减削颗粒的颜色(如果颜色很重要),但不会严重地影响与润滑剂组合的性能;对于特定纤维的最佳剂量通过例如在这种情况下惯用的反复试验来得到。
任何常规上使用的润滑剂可用于粉末金属混合物;且特别受到青睐的润滑剂是那些渗透在霍尔表观密度在2.7到3.5g/cc范围内且霍尔流率在29到35sec/50g范围内的掺合物中的润滑剂。常用润滑剂从由金属皂和蜡(特别是,聚(低碳C1-C5)烯烃蜡和氧化聚(低碳)烯烃均聚物和共聚物、脂肪酸双酰胺和脂肪酸单酰胺)构成的组中选出。优选的蜡是Epolene牌蜡,其名为:E-10,14,15,16,17,20,43;G-3003和G-3015;E-14,20,43;C-10,13,16,17,18;N-10,11,14,15,20,21,30,34,3,可从Eastman Chemical公司购得;和Acumist牌蜡,其名为:A-6,12,18,45;B-6,9,12,18;C-5,12,18;D-5,9;1106,1112,1204,1306,3105,3205,可从Honeywell公司购得。蜡的特定选择依赖于特定金属粉末的物理特征、其将被压紧和脱模的条件以及压紧配件将被烧结的条件。
含有与淀粉颗粒组合的润滑剂的掺合物经常规制备,而无需额外加工工序。混合所述成分,直到形成一基本上均质的掺合物为止,且用所述掺合物填充其中将模制配件的模槽;接着掺合物由锤体压紧,所述锤体配合地且紧密地密接在模槽中,且施加足够的压力(通常在约300到900Mpa(43,500psi或43.5Ksi或21.75Tsi,tons/in2)到1000Mpa(130,500psi或130.5Ksi、或65.25Tsi)的范围内),以形成一生配件;接着所述生配件以一不足以损坏模制配件的完整性的峰值脱模力从模具中脱模,所述力在约453.6到2041.2Kgf(千克力)(1,000到4,500lbf(磅力))的范围内。接着生配件在烧结炉中在惰性空气(通常,氮气和/或氢气)中在高温条件下被烧结,其中所述高温条件高到足以使得润滑剂和一些或全部淀粉颗粒挥发,并形成烧结金属配件。所述炉封装有一烧结带,其以足以提供在炉的热空气(通常具有80%的N2和20%的H2)中的所要时间的速度来移动,在从约1000到2500范围内的区域中烧结带速度在从2.54cm(1″)每分钟到30.5cm(12″)每分钟的范围内。
低合金和预合金配件通常不被热处理,除非其含有充足的石墨来保证热处理。不锈钢配件不被热处理。在下文介绍的大部分说明性实例中,使用小于粉末金属颗粒的淀粉颗粒以避免使得淀粉的尺寸插入额外变量。没有测量只含有淀粉而不含润滑剂的掺合物的表观密度和流率,因为当含有0.75重量%的淀粉颗粒的掺合物由7030.77Kg/cm2(50TSI)的压力来压紧时,该棒不能以可接受量的力从模槽中脱模,这表明淀粉未提供明显的润滑性;因此,具有淀粉而不具有润滑剂的掺合物不会是有用的。另外,只使用基本成分来制造每一掺合物以便集中淀粉颗粒的结果效能。为了集中所有掺合物中的淀粉颗粒的作用,避免使用石墨,除非必须需要石墨来提供烧结配件的所要性质。
实例
由下列实例进一步说明本发明,其中术语“份”指的是重量份,除非另外指出。所有结果都是被同样执行的测试的具有统计价值的数字(通常至少三个)的平均值。不希望下列实例为限制性的,而是希望其仅说明本发明范畴内的一些实施例。
实例1-11
对使用Hoeganaes Ancorsteel 1000B作为原料生铁和各种润滑剂(有些与淀粉颗粒组合)的MPIF F-0000组成物的霍尔表观密度和霍尔流率的估算,其中每一润滑剂或组合具有以(总混合物)重量计的0.75%的量:
在下表1中,每个样品被制备为1lb粉末金属混合物(“掺合物”),其是通过在直径约8cm(3英寸)和约30.5cm(12″)长的圆筒中彻底混合成分来掺合的;接着头尾相覆翻转圆筒30sec,即围绕其中心水平轴头尾相覆旋转;接着用手在多个轴上摇动圆筒30sec。接着再次重复这个进行了超过约90sec的过程以确保大体上的均质性。接着估算每种掺合物的霍尔表观密度。下文所列的具有MPIF F-0000(A1000B)的粉末混合物中的每一者与0.75重量%的改良润滑剂掺合,所述改良润滑剂被指定为常规“润滑剂”和“非润滑剂”的组合,所述“非润滑剂”为微米级淀粉颗粒或微粉化纤维素纤维或者两者。每种掺合物中的每种成分的量以掺合粉末金属混合物的重量百分比给出。
“Allnat C”是微粉化纤维素纤维(确切地说是棉纤维)的内部规定牌号。
“P-105”是熔点在约137℃到138℃(279到281)范围内的市售微米级AcumistA-12聚烯烃蜡(润滑剂)的内部规定牌号,在掺合物5中该蜡单独使用。
在掺合物#4中,P-105与0.375%的淀粉和0.187%的Allnat C一起使用。
所使用的淀粉颗粒是Purity21C,其被一为15百万拉德的剂量照射——其他淀粉颗粒可具有在约2.8g/cc到3.2g/cc范围内的表观密度。每种淀粉的最佳剂量将取决于淀粉来源、其颗粒尺寸和其表面对于不同剂量的照射的反应。
剩余掺合物经指定为与前述规格一致。
接着把由金属粉末制得的掺合物中的每一者填充到常规模具的模槽中,且在足够压力下将其压紧以提供生配件。压紧压力和峰值脱模压力一般在粉末金属配件的大规模生产中可接受的范围内。
通过以下步骤来生产烧结金属配件:把所选润滑剂和非润滑剂成分与铁粉末金属混合以用于生产可压紧混合物;掺合所述成分以形成可在流率的所要范围内流动的均质混合物,把所述混合物加进模槽中;压紧所述混合物以形成生配件,视所使用的粉末金属而定,所述生配件的生坯密度在约6.8g/cc到7.5g/cc的范围内;将所述生物件脱模;并且,在烧结炉中在适于生产烧结金属配件的条件下将其烧结。
表1
掺合物 | 润滑剂类型 | 霍尔表观密度 | 霍尔率 |
编号1234567891011 | %润滑剂/%纤维0.375%Allnat C/0.375%淀粉0.50%Allnat C/0.25%淀粉0.25%Allnat C/0.25%淀粉&0.25%P-1050.187%Allnat C/0.375%淀粉&0.187%P-1050.75%P-1050.75%淀粉0.56%P-105/0.19%纤维0.75%雾化AcrawaxC0.75%硬脂酸锌0.375%淀粉/0.375%P-1050.25%淀粉/0.5%P-105 | g/cc2.792.773.043.042.982.922.973.103.323.103.04 | sec/50g3030242529253031252830 |
从前述数据中可明显地看出,所有掺合物具有一在约27到36sec/50g范围内的可接受的流率。公认一较低流率可需要振动输送来加速混合物的流动。如果把雾化AcrawaxC的表观密度作为标准,且从生产观点来看低于不小于10%(即至少2.69g/cc)的霍尔表观密度是可接受的,那么所有掺合物都将是可接受的,虽然密度在2.9到3.3g/cc范围内是理想的,以便避免加深现有模具。
从前述还可以明显看出,如果把P-105作为标准,那么添加所示量的改良润滑剂增加了霍尔表观密度,这是出乎意外的。
接着以7030.77Kg/cm2或50TSI(吨/平方英尺)来把每种掺合物压紧成标准测试棒,每一者为3.175cm(1.25″)长×1.27cm(0.5″)宽×0.635cm(0.25″)厚,以估算每一润滑剂对可压缩性和生坯强度的作用。此后,在烧结带上烧结所有棒,所述烧结带在常规烧结炉中在80%氮气/20%氢气的气氛中以约12.7cm/min(5″/min)的速度移动通过温度为649℃(1200)、760℃(1400)、1121℃(2050)和1121℃(2050)的连续区域;且估算所述烧结棒的性质。
将了解到,所使用的改良润滑剂的量以及润滑剂与非润滑剂的比例的选择将取决于被压紧的特定粉末金属混合物和烧结配件的(待满足的)规格。组合量或一种组份相对于另一种组份的比例太高或太低将导致掺合物的表观密度和流率超出所要参数的范围。一般来说,当改良润滑剂的存在量小于0.5重量%或大于1.5重量%时,掺合物在生产过程中不是十分有用;因此,该量优选地不大于1.5重量%,且更优选地不大于1重量%。
估算由以上表1中数字标志的掺合物制得的棒的生坯密度、生坯强度和需要用来把棒从模槽中脱模的峰值脱模压力。接着在装备有烧结带的烧结炉中烧结所述棒,所述烧结带以8.9cm(3.5″)每秒的速度移动穿过具有连续较高温度的区域以提供在炉的97%N2/3%H2的热气氛中的所要时间,在穿过648.9℃(1200)、760℃(1400)、1121℃(2050)和1121℃(2050)的四个主要温度区域时烧结带速度在从2.54cm(1″)/min到30.5cm(12″)/min的范围内。每个区域的长度接近3米(7′7″)。
测量至少三个样品的烧结密度、烧结TRS、烧结表观Rockwell F硬度(HRF)和烧结尺寸一致性(DC),并求出其平均值。
在下表2中给出结果:
表2
掺合物编号 | 生坯密度g/cc@7+KKg/cm2 | 生坯强度MPa(psi)@7+K Kg/cm2 | 峰值脱模压力Kgf(lbf)@7+K Kg/cm2 | 烧结密度,g/cc | 烧结TRSMPa(Ksi) | 烧结表观硬度HRF | 烧结DC,%与模具尺寸不同 |
1 | 7.06 | 28.8(4185) | 2743(6046) | 7.11 | 559(81.2) | 72 | 0.17 |
2 | 7.15 | 30.67(4452) | 3262(7191) | 7.11 | 588(85.3) | 73 | 0.15 |
3 | 7.10 | 27.31(3964) | 1383(3048) | 7.15 | 582(84.5) | 72 | 0.16 |
4 | 7.06 | 25.53(3706) | 1456(3210) | 7.09 | 548(79.6) | 71 | 0.16 |
5 | 7.13 | 25.45(3694 | 1267(2793) | 7.11 | 455(66.1) | 59 | 0.26 |
6 | 7.01 | 31.15(4521) | 3195(7042) | 7.07 | 589(85.5) | 70 | 0.22 |
7 | 7.13 | 24.07(3493) | 1577(3476) | 7.12 | 599(87.) | 73 | 0.15 |
表2(续)
掺合物编号. | 生坯密度g/cc@7+KKg/cm2 | 生坯强度MPa(psi)@7+K Kg/cm2 | 峰值脱模压力Kgf(Ibf)@7+KKg/cm2 | 烧结密度,g/cc | 烧结TRSMPa(Ksi) | 烧结表观硬度HRP | 烧结DC,%与模具尺寸不同 |
8 | 7.16 | 17.2(2496) | 1247(2749) | 7.16 | 508(73.7) | 65 | 0.18 |
9 | 7.12 | 14.65(2127) | 1196(2636) | 7.11 | 508(73.7) | 61 | 0.29 |
10 | 7.04 | 28.9(4200) | 1543(3401) | 7.08 | 560(81.3) | 69 | 0.17 |
11 | 7.10 | 29.53(4287) | 1409(3106) | 7.07 | 549(79.7) | 67 | 0.12 |
在上表中,7+K Kg/cm2指的是7,030.8Kg/cm2压力=50tons/in2(TSI),且Mpa指的是兆帕斯卡,其中1Mpa=1000Kpa
从前述结果中可明显看到,掺合物#1到#7和#10&11的生坯强度是掺合物#8(Acrawax C)和9(硬脂酸锌)的生坯强度的两倍。虽然掺合物#1、2和6的峰值脱模压力是掺合物#8和9的峰值脱模压力的两倍,但掺合物#10和11的峰值脱模压力(即起始一模制配件离开模槽所需的力,由测压仪测量得)只高了约25%。所有脱模压力都在可接受范围内。
还可以明显看到,由新颖烧结掺合物制得的所有棒的横向断裂强度(TRS)和表观Rockwell F硬度高于由硬脂酸锌、Acrawax和Acumist制得的烧结棒的TRS和表观Rockwell F硬度。此外,新颖烧结棒具有最好的尺寸一致性(DC),即最小变形。
以此提供相关主题的大体揭示并详细描述新颖改良润滑剂和粉末金属混合物,且以具有制造和使用本发明的最佳模式的特定实施例来说明本发明,将了解到将不因为所说明和描述的特定实施例来强加任何不适当的限定,确切地说,不将本发明限制于本文阐述的细节的盲目依附中。
Claims (16)
1.一种粉末金属混合物,其包含铁金属粉末和改良润滑剂,所述改良润滑剂基本上由(i)润滑剂粉末和(ii)具有小于150μm的平均当量直径(average equivalentdiameter)的淀粉颗粒构成,所述改良润滑剂以小于组成物重量计的2%的量存在,所述混合物具有:(i)在数值上比由不具有所述淀粉颗粒的常规润滑剂制得的相同粉末金属混合物获得的霍尔表观密度小不小于10%的霍尔表观密度;和(ii)在约25到40sec/50g混合物的范围内的霍尔流率。
2.如权利要求1所述的混合物,其中所述淀粉颗粒具有小于50μm的平均当量直径,且所述润滑剂粉末是从由脂肪酸单酰胺、脂肪酸双酰胺、金属皂和聚烯烃蜡构成的组中选出。
3.如权利要求1所述的混合物,其中约90重量%的淀粉颗粒具有在5到50μm范围内的平均当量直径;5重量%到40重量%具有在2到20μm范围内的平均当量直径;且所述淀粉具有在2.8到3.2g/cc范围内的霍尔表观密度,且所述混合物的霍尔流率在约25到35sec/50g混合物的范围内。
4.如权利要求1所述的混合物,其包括碎片纤维素纤维,所述纤维具有小于150μm的平均长度和在约1μ到20μ范围内的直径,且以不大于所述淀粉颗粒的量存在。
5.如权利要求4所述的混合物,其中所述改良润滑剂优选地在0.25重量%到1重量%的范围内,且淀粉润滑剂中润滑剂/淀粉和润滑剂/(淀粉+纤维素碎片)(若存在)的重量比在约1∶2到10∶1、优选地在1∶1到4∶1的范围内。
6.如权利要求1所述的改良润滑剂,其中所述淀粉颗粒由10到30百万拉德(MegaRad)的γ辐射照射。
7.如权利要求6所述的改良润滑剂,其包括碎片纤维素纤维,所述纤维具有小于150μm的平均长度和在约1μ到20μ范围内的直径,以不大于所述淀粉颗粒的量存在,且所述淀粉颗粒由约15百万拉德的γ辐射照射。
8.如权利要求7所述的改良润滑剂,其中所述碎片纤维素纤维已被暴露到电子束辐射以接收在约30到100百万拉德范围内的剂量。
9.一种包括润滑剂的粉末状铁金属混合物,所述混合物具有在约25到40sec/50g混合物范围内的霍尔流率,改进包含改良润滑剂,其基本由下列物质构成:(i)润滑剂粉末和(ii)淀粉颗粒,其具有小于150μm的平均当量直径且以所述混合物重量计约0.25%到小于0.75%的量存在;和(iii)碎片纤维素纤维,其具有小于150μm的平均长度和约1μ到20μ范围内的直径且以所述混合物重量计的0%到小于0.75%的量存在,但不多于所述存在的淀粉,所述改良润滑剂以小于组成物重量计的1.5%的量存在,所述混合物具有(i)在数值上比由不具有所述淀粉颗粒的常规润滑剂制成的相同粉末金属混合物获得的霍尔表观密度小不小于10%的霍尔表观密度,淀粉润滑剂中的润滑剂/淀粉和润滑剂/(淀粉+纤维素碎片)(若存在)的重量比在约1∶2到10∶1、优选地在1∶1到4∶1范围内。
10.如权利要求9所述的混合物,其中所述淀粉颗粒被10到30百万拉德的γ辐射照射,且所述碎片纤维素纤维已被暴露到电子束辐射以接收在约30到100百万拉德范围内的剂量,且所述霍尔流率在约25到35sec/50g混合物的范围内。
11.一种用于制造均质铁粉末金属混合物的方法,其包含
把具有小于约150μm的平均颗粒直径的金属颗粒与改良润滑剂组合,所述改良润滑剂基本上由下列物质构成:(i)润滑剂粉末和(ii)淀粉颗粒,所述颗粒具有小于150μm的平均当量直径,所述改良润滑剂以小于组成物重量计的2%的量存在,所述混合物具有:(i)在数值上比由不具有所述淀粉颗粒的常规润滑剂制成的相同粉末金属混合物获得的霍尔表观密度小不小于10%的霍尔表观密度;和(ii)在约25到40sec/50g混合物范围内的霍尔流率,和
在模具中压紧所述混合物以形成压紧生坯物件。
12.如权利要求11所述的方法,其中所述霍尔表观密度大于由不具有所述淀粉颗粒的常规润滑剂制得的相同粉末金属混合物获得的霍尔表观密度,且所述霍尔流率在约25到35sec/50g混合物的范围内。
13.一种适合于粉末金属物件中使用的改良润滑剂,所述改良润滑剂基本上由与淀粉颗粒组合的润滑剂构成,所述润滑剂从由无机化合物、金属有机化合物和蜡构成的组中选出,所述润滑剂具有小于50μm的平均颗粒直径,其中约90重量%的淀粉颗粒具有在5到50μm范围内的平均当量直径;5重量%到40重量%具有在2到20μm范围内的平均当量直径;所述淀粉具有在2.8到3.2g/cc范围内的霍尔表观密度。
14.如权利要求13所述的改良润滑剂,其中所述淀粉颗粒被10到30百万拉德的γ辐射照射。
15.如权利要求14所述的改良润滑剂,其包括碎片纤维素纤维,所述纤维具有小于150μm的平均长度和在约1μ到20μ范围内的直径,且以不多于所述淀粉颗粒的量存在。
16.如权利要求15所述的改良润滑剂,其中所述碎片纤维素纤维已被暴露到电子束辐射以接收在约30到100百万拉德范围内的剂量。
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US9522964B2 (en) | 2012-04-03 | 2016-12-20 | Development, Inc. | Micronized starch and methods for manufacturing same |
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CA2553471A1 (en) | 2005-08-04 |
TWI289601B (en) | 2007-11-11 |
KR20060103958A (ko) | 2006-10-04 |
AU2004314326A1 (en) | 2005-08-04 |
JP2007517984A (ja) | 2007-07-05 |
DE602004022998D1 (de) | 2009-10-15 |
EP1730321B1 (en) | 2009-09-02 |
US20040144206A1 (en) | 2004-07-29 |
ATE441734T1 (de) | 2009-09-15 |
EP1730321A1 (en) | 2006-12-13 |
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