CN1303751A - 生产粉末冶金产品或陶瓷产品的模塑组合物 - Google Patents
生产粉末冶金产品或陶瓷产品的模塑组合物 Download PDFInfo
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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Abstract
本发明涉及一种基于可烧结材料的模塑组合物,含有a)80—99.5%(重量)最大粒度为2000微米的可烧结的粉末,b)0.5—20%(重量)金属茂聚烯烃蜡,c)如果需要,直到19.5%(重量)的另外干润滑剂,以及涉及通过压制来生产成型的陶瓷的和粉末冶金的部件的应用。
Description
本发明涉及一种粉末冶金的或陶瓷的模塑组合物，它通过干压成型以及用金属茂聚烯烃蜡为基础的润滑剂来生产和加工。
粉末冶金产品或陶瓷产品的原料是可自由流动的并与粉状润滑剂混合的金属粉末或陶瓷粉末。将这种含润滑剂的混合物送入压模，并经轴向或等压压制，形成成型体。通过称为脱润滑剂的热加工，使成型体释放出润滑剂以后，粉末压制品经烧结，得到经烧结的部件。
正如WO-A-98/05453中公开的，脂肪酸或其金属盐，例如硬脂酸锌或硬脂酸锂可用来生产粉末模塑组合物，并将这些组合物进行粉末冶金加工。特别是，这些产品中润滑剂作用是很好的。但是，这些材料的热解性质有缺点。当热分解时，金属残留物或氧化残留物留在炉中或留在烧结的部件上或留在烧结的部件中。它使清理的费用增加或使烧结产品的质量下降。
使用没有残留物并有满意的润滑剂作用的酰胺蜡是可能的。但是，酰胺蜡的使用对粉末/润滑剂混合物的流动性有不良影响。它们的使用被限制到在冷的条件下，即在100℃以下的温度下使用。
WO-A-99/28067提出聚酯用作润滑剂。但是，这些干润滑剂的可用性仅在100℃以上是令人满意的，还必须用其他润滑剂例如硬脂酸锌或酰胺蜡改进。
WO-A-99/11406公开了Mw为500-10000的烯烃聚合物的应用。
但是已发现，特别是由于它们的粘度性质，给定的润滑剂有许多缺点，特别是在热压中。在100℃以上的温度下，使得粉末/润滑剂混合物的流动性变坏。这就对装填压模时的堆积密度有不良影响，因此使随后的压制过程变坏。
令人吃惊地发现，用金属茂催化剂制备的聚烯烃蜡(“金属茂聚烯烃蜡”)特别适合在粉末冶金的和陶瓷的模塑组合物中用作润滑剂。此外，还发现，用金属茂催化剂制备的熔点为80-120℃的聚烯烃蜡特别适用于冷压制，而用金属茂催化剂制备的熔点为100-165℃的聚烯烃蜡特别适用于热压制。
因此，本发明提供一种基于可烧结的材料的模塑组合物，它含有a)80～99.5％(重量)最大粒度为2000微米的可烧结的粉末；b)0.5～20％(重量)金属茂聚烯烃蜡；c)如果需要，直到19.5％(重量)其他干润滑剂。
本发明的模塑组合物含有非金属无机粉末形式或金属粉末形式的可烧结的材料。它们包括基于瓷器料、硅酸锆、金属氧化物、金属氮化物和金属碳化物的粉末。
可用于本发明目的的金属粉末是基于铁、钨、铜、青铜、钼、铬或镍的化合物的粉末。粉末的最大粒度优选为1000微米。模塑组合物优选含有85-99％(重量)可烧结的材料。
本发明的模塑组合物还含有金属茂聚烯烃蜡作为干润滑剂。这种金属茂聚烯烃蜡优选具有以下性质：
滴点(Tp)： 80-165℃
酸值(Sz)： 0-50毫克KOH/克
密度： 0.87-1.03克/厘米3
170℃下熔体的粘度： 10-100000mPas
模塑组合物优选含有1-15％(重量)金属茂聚烯烃蜡。
可能的聚烯烃蜡为乙烯或丙烯的均聚物或乙烯或丙烯相互聚合的或与一种或多种1-烯烃的共聚物。所用的1-烯烃为C4-C18、优选C4-C6的直链或支链烯烃。这些烯烃可有与烯属双键共轭的芳族取代基。其例子是1-丁烯、1-己烯、1-辛烯或十八烯和苯乙烯。优选乙烯与丙烯或1-丁烯的共聚物。共聚物含有70-99.9％(重量)、优选80-99％(重量)乙烯。
特别适用的聚烯烃蜡是那些滴点为90-160℃、优选100-155℃,140℃下的熔体粘度为10-10000mPas、优选50-5000mPas和20℃下的密度为0.89-0.96克/厘米3、优选0.91-0.94克/厘米3的聚烯烃蜡。
用于生产聚烯烃蜡的金属茂催化剂是分子式为M1Lx的手性的或非手性的过渡金属化合物。过渡金属化合物M1Lx含有至少一个中心金属原子M1，而至少一个π配体例如环戊二烯基配体键联在中心金属原子M1。此外，取代基例如卤素原子或烷基、烷氧基或芳基可键联到中心金属原子M1上。M1优选为元素周期表第Ⅲ、Ⅳ、Ⅴ或Ⅵ主族的元素，例如Ti、Zr或Hf。对于本发明来说，环戊二烯基配体为未取代的环戊二烯基和取代的环戊二烯基，例如甲基环戊二烯基、茚基、2-甲基茚基、2-甲基-4-苯基茚基、四氢茚基或八氢芴基。这些π配体可为桥联的或非桥联的，单桥和多桥、包括通过环系的桥是可能的。术语“金属茂”还包括有一个以上金属茂骨架的化合物，称为多环金属茂。它们可有任何的取代模型和桥联形式。这样的多环金属茂的单个金属茂骨架彼此可为相同的或不同的。这样的多环金属茂的例子例如在EP-A-0632063中公开。金属茂的结构通式及其用共催化剂活化的例子例如在EP-A-0571882中公开。另一些适合的蜡是通过氧化改性的金属茂蜡，例如通过用空气处理蜡熔体制得的金属茂蜡，如在EP-A-0896591中公开的。在这三篇专利中的有关公开内容在这里作为参考并入。
本发明的模塑组合物可含有另外的干润滑剂。它们优选为脂肪酸的金属盐或酰胺蜡，例如硬脂酸锂、硬脂酸钙或硬脂酸锌或乙烯双(硬脂酸基酰胺)或硬脂酰基酰胺型的酰胺蜡。
本发明的模塑组合物的生产和加工通常按以下方式进行：1．混合：在10-150℃下，将可烧结的粉末在混合器中与通过研磨或熔体喷雾粉化的聚烯烃蜡混合，一直到制得均匀的自由流动的模塑组合物。2．压制：将由1制得的20-160℃的模塑组合物放在20-160℃的模中，然后在高达700兆帕的压力下使模塑组合物成型，得到成型的部件。3．脱粘合剂：为了用热解的方法除去金属茂聚烯烃蜡，在适合的气体气氛中将由2制得的成型的部件缓慢加热到600℃。4．烧结：将脱除粘合剂的成型部件优选在相同的炉中在材料特定的烧结温度下烧结。
本发明还提供本发明的模塑组合物通过压制生产成型的陶瓷的和粉末冶金的部件的应用。
用以下实施例说明本发明：
实施例1
将0.8份重金属茂乙烯-丙烯共聚物蜡(Tp:110℃、Sz:20毫克KOH/克、170℃下粘度：2000mPas)粉碎到粒度小于60微米和平均粒度为20微米，然后与99.2重份铁粉ASC 100.29(制造商：Hgans AB)在室温下混合15分钟。制得的混合物的滴流速度为30秒/50克(按钢/铁试验方法用流速计测量的)，而堆积密度为2.95克/厘米3。在600兆帕的压力下冷压，得到尺寸为11.2×20毫米的圆柱体。压制的密度为7.20克/厘米3。在流动氢气中脱粘合剂以后，将圆柱体在1120℃下在氢气中烧结30分钟，得到的密度为7.45克/厘米3。
实施例2
将1重份金属茂聚丙烯蜡(Tp:160℃、Sz:0毫克KOH/克、170℃粘度：3500mPas)粉碎到粒度小于60微米和平均粒度为20微米，然后在130℃下与99重份铁粉ASC 100.29(制造商：Hgans AB)混合15分钟。将制得的混合物放入加热到150℃的模中，然后在600兆帕压力下热压。生产的11.2×20毫米圆柱体的压制密度为7.30克/厘米3。将圆柱体在高达600℃下在流动氢气中脱粘合剂，然后在1120℃下在氢气中烧结30分钟，得到的密度为7.50克/厘米3。
实施例3
将5重份经氧化的金属茂聚乙烯蜡(Tp:110℃、Sz:15毫克KOH/克、170℃粘度：3000mPas)粉碎到粒度为150-450微米，然后与95重份粒度为800-1500微米的陶瓷结合氧化铝混合，再在200兆帕下在室温下压制成圆柱体。圆柱体的密度为2.6克/厘米3。湿强度为3牛/毫米2。在空气中使圆柱体脱粘合剂，然后在1000℃下焙烧，得到密度为3.1克/厘米3的多孔体。
Claims (5)
1．一种基于可烧结材料的模塑组合物，它含有a)80-99.5％(重量)最大粒度为2000微米的可烧结粉末，b)0.5-20％(重量)金属茂聚烯烃蜡，c)如果需要，直到19.5％(重量)的另外干润滑剂。
2．根据权利要求1的模塑组合物，它含有85-99％(重量)组分a)。
3．根据权利要求1和/或2的模塑组合物，它含有1-15％(重量)组分b)。
4．根据权利要求1-3中一项或多项的模塑组合物，它含有脂肪酸的金属盐或酰胺作为组分c)。
5．根据权利要求1-4中一项或多项的模塑组合物的应用，用于通过压制来生产成型的陶瓷的和粉末冶金的部件。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19960991A DE19960991C1 (de) | 1999-12-17 | 1999-12-17 | Formmasse zur Herstellung pulvermetallischer oder keramischer Erzeugnisse |
| DE19960991.8 | 1999-12-17 |
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| CN1303751A true CN1303751A (zh) | 2001-07-18 |
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| CN00136615A Pending CN1303751A (zh) | 1999-12-17 | 2000-12-15 | 生产粉末冶金产品或陶瓷产品的模塑组合物 |
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| US (1) | US6383281B2 (zh) |
| EP (1) | EP1108487A3 (zh) |
| JP (1) | JP2001214204A (zh) |
| CN (1) | CN1303751A (zh) |
| CA (1) | CA2328630A1 (zh) |
| DE (1) | DE19960991C1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321973A (zh) * | 2017-07-05 | 2017-11-07 | 北京科技大学 | 一种粉末冶金用润滑剂的制备及粘结混合粉末制造方法 |
| US11128247B2 (en) | 2017-01-06 | 2021-09-21 | Thermo King Corporation | DC to DC converter sourcing variable DC link voltage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10106172A1 (de) * | 2001-02-10 | 2002-08-29 | Bosch Gmbh Robert | Verfahren zur Herstellung eines Formteils aus einem weichmagnetischen Verbundwerkstoff |
| DE10216118A1 (de) * | 2002-04-12 | 2004-04-22 | Clariant Gmbh | Verwendung von Metallocenwachsen in Pulverlacken |
| DE10338344A1 (de) * | 2003-08-21 | 2005-03-24 | Clariant Gmbh | Modifizierte Polyolefinwachse |
| US7845185B2 (en) * | 2004-12-29 | 2010-12-07 | York International Corporation | Method and apparatus for dehumidification |
| DE102004050770A1 (de) * | 2004-10-19 | 2006-04-27 | Clariant Gmbh | Verfahren zur Herstellung oder Bearbeitung von Hohlkörpern |
| PT104258B (pt) * | 2008-11-20 | 2012-01-24 | Ct Tecnologico Da Ceramica E Do Vidro | Ligantes poliméricos à base de um polímero solúvel em água e um polímero de estrutura para utilização em moldação por injecção de pós metálicos ou cerâmicos e processo para a sua produção |
| CN101695808B (zh) * | 2009-10-27 | 2013-04-24 | 重庆泰蒙科技有限公司 | 带孔陶瓷刀片的制备方法 |
| DE102014108820A1 (de) * | 2014-06-24 | 2015-12-24 | Hib Trim Part Solutions Gmbh | Verfahren zum Herstellen eines naturfaserverstärkten Kunststoffteils |
| CN107337427B (zh) * | 2016-11-29 | 2020-03-17 | 佛山市东鹏陶瓷有限公司 | 一种干粉陶瓷砖及其坯体的制备方法和成品 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5264681A (en) * | 1991-02-14 | 1993-11-23 | Ngk Spark Plug Co., Ltd. | Ceramic heater |
| JP3004800B2 (ja) * | 1991-03-27 | 2000-01-31 | 川崎製鉄株式会社 | 粉末冶金用鉄基粉末混合物及びその製造方法 |
| DE59305691D1 (de) | 1992-05-26 | 1997-04-17 | Hoechst Ag | Verfahren zur Herstellung von Polyolefinwachsen |
| US5372980A (en) * | 1993-06-03 | 1994-12-13 | Polysar | Bimetallic metallocene alumoxane catalyst system and its use in the preparation of ethylene-alpha olefin and ethylene-alpha olefin-non-conjugated diolefin elastomers |
| CN1050786C (zh) * | 1994-03-15 | 2000-03-29 | 伊藤南己 | 蜡状物质和使用蜡状物质的造型方法 |
| DE4446923A1 (de) * | 1994-12-28 | 1996-07-04 | Hoechst Ag | Polyolefinwachs |
| DE19617230A1 (de) * | 1996-04-30 | 1997-11-06 | Basf Ag | Oxidierte Metallocen-Polyolefin-Wachse |
| JPH1046202A (ja) * | 1996-08-06 | 1998-02-17 | Nitto Kasei Kogyo Kk | 粉末冶金用の粉末潤滑剤 |
| SE9703151D0 (sv) * | 1997-09-01 | 1997-09-01 | Hoeganaes Ab | Lubricant for metallurgical powder compositions |
| DE19750663A1 (de) * | 1997-11-15 | 1999-05-20 | Clariant Gmbh | Verwendung von Polyolefinwachsen in Lösemittelpasten |
| SE9704494D0 (sv) * | 1997-12-02 | 1997-12-02 | Hoeganaes Ab | Lubricant for metallurgical powder compositions |
| US6221289B1 (en) * | 1998-08-07 | 2001-04-24 | Core-Tech, Inc. | Method of making ceramic elements to be sintered and binder compositions therefor |
-
1999
- 1999-12-17 DE DE19960991A patent/DE19960991C1/de not_active Expired - Fee Related
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2000
- 2000-11-01 JP JP2000334099A patent/JP2001214204A/ja active Pending
- 2000-12-06 EP EP00126749A patent/EP1108487A3/de not_active Withdrawn
- 2000-12-15 US US09/738,616 patent/US6383281B2/en not_active Expired - Fee Related
- 2000-12-15 CN CN00136615A patent/CN1303751A/zh active Pending
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11128247B2 (en) | 2017-01-06 | 2021-09-21 | Thermo King Corporation | DC to DC converter sourcing variable DC link voltage |
| CN107321973A (zh) * | 2017-07-05 | 2017-11-07 | 北京科技大学 | 一种粉末冶金用润滑剂的制备及粘结混合粉末制造方法 |
Also Published As
| Publication number | Publication date |
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| DE19960991C1 (de) | 2001-03-22 |
| CA2328630A1 (en) | 2001-06-17 |
| EP1108487A3 (de) | 2004-03-03 |
| US6383281B2 (en) | 2002-05-07 |
| JP2001214204A (ja) | 2001-08-07 |
| US20010004138A1 (en) | 2001-06-21 |
| EP1108487A2 (de) | 2001-06-20 |
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