CN1070094C - 钴金属粉末 - Google Patents

钴金属粉末 Download PDF

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CN1070094C
CN1070094C CN94112792A CN94112792A CN1070094C CN 1070094 C CN1070094 C CN 1070094C CN 94112792 A CN94112792 A CN 94112792A CN 94112792 A CN94112792 A CN 94112792A CN 1070094 C CN1070094 C CN 1070094C
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metal powder
cobalt metal
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M·赫内
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • 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
    • 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
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other

Abstract

本发明涉及作为用于制备金刚石工具和/或硬质合金工具和/或耐磨敷层的粘结金属的钴金属粉末，并涉及由其生产的复合烧结制品。

Description

钴金属粉末
本发明涉及用作制备金刚石工具和/或硬质合金工具和/或耐磨敷层的粘结金属的钴金属粉末，并涉及由其生产的复合烧结制品。
已知钴金属粉末可通过熔融金属雾化来生产。日本专利申请书53-093165叙述了雾化钴金属的生产和使用。根据该文献，通过研磨和激波回火处理收集的雾化粗制品，以获得希望的六方晶相/立方晶相的比例。研磨工序增加钴金属粉末的成本，也是杂质来源。
虽然钴金属粉末可通过熔体雾化非常便宜地生产，但用该方法获得的粉末完全不适合用作粘结金属，例如用于生产金刚石工具，因为由于球状颗粒形状和颗粒尺寸在一般的800-900℃烧结温度下不能形成足够硬度的致密的复合烧结制品。
雾化钴金属粉末的热压复合烧结制品性能不令人满意主要归因于预压坯的压缩度不足，这是由于球状颗粒形状，相对窄的颗粒尺寸分布和粗糙的初级颗粒(图2)。通过热压也不能获得所需的至少8.5g/cm3的密度。
对比起来，在高温下用氢还原含氧钴化合物可获得适合用作基质材料的FSSS值3-5μm的所谓400目粉末(图1中)的钴金属粉末。通过400目筛从接受的粉末获得这种名称的粉末。这种粉末可满足作复合材料基质金属所期待的满意的硬度和烧结密度的要求。但是，400目粉末具有非常高的杂质比率。众所周知，铝、钙、钠、镁和硅很容易同钴金属粉末的氧形成稳定的氧化物。这些稳定的氧化物能在金刚石切片中引起不希望的孔隙。
在硬质合金情况下，如果超量存在上述杂质和硫，诱发的孔隙降低强度。所以，对两种用途都需要低杂质含量的钴金属粉末。根据在冶金初级阶段中进行的纯化工作量，钴金属粉末的纯度可改善而满足要求。用于生产特纯钴金属粉末的费用当然很大，所以这种粉末非常贵。
本发明的目的是提供不具有任何上述粉末的缺点的钴金属粉末。
现发现呈现所需性能的钴金属粉末。本发明涉及一种可用作制备金刚石工具和/或硬质合金工具和/或耐磨敷层的粘结金属的二组分的结晶钴金属粉末，其特征在于第一种组分为20-80％(重量)的包括光学测定颗粒尺寸为5-150μm的雾化钴金属粉末，第二种组分为余量的包括光学测定初级颗粒尺寸小于3μm的还原钴金属粉末。
从下面结合附图对优选实施方案的详细叙述可明显看出其它的目的、特别和优点。
图1-4是扫描电镜显微金相照片(1000×20kv)，包括现有技术粉末(图1-还原氧化钴粉末)，水雾化钴粉末(图2-见下面实施例2)，按照本发明优选实施方案的二组分钴粉末(图3-见实施例2)和用二组分钴粉末热压制品的表面(图4-见实施例2)。
本发明钴金属粉末具有从氧化物或含氧化合物还原获得的钴金属粉末的有价值优点，并含更少量的上述关键性杂质。在优选的实施方案中，含小于20ppm的Al，小于20ppm的Ca，小于30ppm的Na，小于20ppm的Mg，小于30ppm的S和小于75ppm的Si。
本发明钴金属粉末是雾化的钴金属粉末与用氢还原的细钴粉末的混合物。
虽然本发明钴金属粉末在技术使用上的高适用性实际上在于混合物中含量的20％(重量)为用氢还原的雾化细钴金属粉末，从有价值意义的观点看，该含量上限直到80％(重量)还是允许的。该混合物的粉末冶金特性在上述限制内也是良好的。
雾化钴金属粉末的量优选30-70％(重量)。水雾化的主要为球状的钴金属粉末和气雾化的主要是球状的钴金属粉末都适合用作雾化钴金属粉末。
结晶钴金属粉末优选具有BET表面大于0.8m2/g(用氮1-点方法(DIN66131)测定)。在一个优选的实施方案中，本发明钴金属粉末具有小于1.4kg/cm3的松装密度。
利用本发明钴金属粉末有利的颗粒尺寸分布的优点，热压后可获得至少8.5g/cm3的密度，致使该粉末特征在于极好的压缩度。在本发明钴金属粉末的另一个优选的实施方案中，在热压试板上测量时，该粉末洛氏硬度至少为98HRB。
本发明钴金属粉末很合适粉末治金制备金刚石工具和/或硬质金属，其中钴任选的与其它一般基质金属一起是粘结相。
所以，本发明也涉及由硬质合金粉末和/或金刚石粉末和粘结金属制备的复合烧结制品，本发明的钴金属粉末任意地同其它金属粉末一起被用作粘合性金属。
下面的实施例非限制性的描述本发明。实施例1(70∶30混合物)
将0.7kg平均颗粒尺寸1.7μm的通过63μm筛网过筛，其松装密度为1.2g/cm3(图1)的细钴金属粉末(用氢还原氧化钴得到)在“Turbula”混合器中同0.3kg通过38μm筛网，其松装密度3.3g/cm3(图2)的水雾化钴金属粉末(11.7μmFSSS)混合1小时。这样获得的产品具有FSSS值2.2μm且松装密度为0.73g/cm3。同现有技术的400目钴金属粉末相比，关键杂质含量明显降低(表2)。烧结试验
对于烧结试验，将混合的粉末加到直径约30mm的圆形石墨模中并在下列条件下热压：加热梯度：180k/分烧结温度：830℃(在石墨模中测量)烧结压力：350N/mm2保温时间：3分钟
这样获得的试板最终密度为8.54g/cm3，硬度(洛氏B)为101.6HRB。实施例2(60∶40混合物)
将0.6kg BET表面为1.11m2/g，平均颗粒尺寸为1.7μm(FSSS)，通过63μm筛网过筛的，松装密度为1.2g/cm3(图1)的细钴金属粉末在犁片混合器中同0.4kg BET表面为0.73m2/g(通过氮1-点法(DIN66131)测定)，通过38μm筛网过筛的，松装密度为3.3g/cm3(图2)的水雾化钴金属粉末(11.7μm FSSS)混合60分钟。获得的钴金属粉末(图3)具有FSSS值为2.6μm，BET面为0.74m2/g，且松装密度为0.8g/cm3。同一般的400目钴金属粉末相比化学杂质含量明显降低(表2)。
实施例1所述热压试板密度为8.54g/cm3，硬度为101.2HRB。图4清楚地表明在抛光和腐蚀的试样中，大的圆形钴颗粒在细初晶中仍是完整的。实施例3(50∶50混合物)
将0.5kg平均颗粒尺寸0.9μm,BET表面为1.85m2/g，通过100μm筛网过筛的(松装密度0.8g/cm3)的细钴金属粉末(由氢氧化钴还原获得)在“Turbula”混合器中同0.5kg BET表面为0.73m2/g的水雾化钴金属粉末(11.7μm FSSS)混合15分钟。获得的混合物FSSS值为1.5μm FSSS，BET面为1.06m2/g，松装密度为0.8g/cm3。
实施例1中，在热压试板上测得硬度为100.4HRB，密度为8.5g/cm3。比较例1(100％水雾化钴金属粉末＜63μm)
按照实施例1，将通过63μm筛网过筛的，FSSS值为12μm的纯水雾化钴金属粉末热压，热压温度不同。在按下面条件获得的试板上测得下列硬度值：热压烧结试验加热梯度：180k/分烧结压力：350N/mm2保持时间：3分钟结果：
烧结温度     硬度值(HRB)    密度
 800℃850℃900℃950℃ 压碎，不能测硬度254047   未测出7.07.57.8
在任何情况下雾化钴金属粉末也不能达到要求的最小密度8.5g/cm3或最小硬度98HRB。
实施例5(100％水雾化钴金属粉未＜38μm)
在按照实施例1所述的条件下将通过38μm筛网过筛的(图2)，FSSS值为11.8μm的纯水雾化钴金属粉末热压，在试板上测出硬度为80HRB。
尽管更细地过筛，仍不可能达到要求的最小密度或最小硬度。
实施例1-3的数据和涉及400目钴粉末和雾化粉末(根据现有技术)的比较数据均列入表1。
                          表1(硬度试验结果)
热压温度                              烧结密度/洛氏硬度(HRB)
℃ 实施例5的雾化Co粉末 实施例1(70/30)的混合物 实施例2(60/40)的混合物 实施例3(50/50)的混合物 现有技术的400目Co
830  8.1g/cm380HRB  8.54g/cm3101.6HRB 8.54g/cm3101.2HRB  8.5g/cm3100HRB  8.45g/cm397.7HRB
比较例(400目粉末)表2：在钴金属粉末中关键杂质的比较数据
同一般400目钴金属粉末比较，关键杂质含量显著降低(表2)。
400目钴(400目钴金属粉末(“Cobalt Powder400-mesh”,Hoboken Overpelt的产品，Belgium))和本发明实施例1、2和3的混合物：
杂质 400目CO(100/0) 实施例1(70/30)的混合物 实施例2(60/40)的混合物 实施例3(50/50)的混合物
 Al(ppm) 180  6  7  6
 Ca(ppm) 320  12  12  13
 Na(ppm) 55  25  22  9
 Mg(ppm) 150  8  8  3
 S(ppm) 140  13  14  15
 Si(ppm) 310  34  36  41

Claims (12)

1．一种可用作制备金刚石工具和/或硬质合金工具和/或耐磨敷层的粘结金属的二组分的结晶钴金属粉末，其特征在于第一种组分为20-80％(重量)的包括光学测定颗粒尺寸为5-150μm的雾化钴金属粉末，第二种组分为余量的包括光学测定初级颗粒尺寸小于3μm的还原钴金属粉末。
2．按照权利要求1的钴金属粉末，其特征在于雾化钴金属粉末的量为30-70％(重量)。
3．按照权利要求1或2的钴金属粉末，其特征在于第二种组分是团聚的。
4．按照权利要求3的钴金属粉末，其特征在于用氮1-点法(DIN66131)测量的结晶钴金属粉末的BET表面大于0.8m2/g。
5．按照权利要求4的钴金属粉末，其特征在于雾化的钴组分主要是球状的。
6．按照权利要求1或2的钴金属粉末，其特征在于雾化钴金属粉末是主要为球状的水雾化钴金属粉末。
7．按照权利要求1或2的钴金属粉末，其特征在于雾化钴金属粉末是主要为球状的气雾化钴金属粉末。
8．按照权利要求1或2的钴金属粉末，其特征在于其松装密度小于1.4g/m3。
9．按照权利要求1或2的钴金属粉末，其特征在于它含小于20ppm铝、小于20ppm钙、小于30ppm钠、小于20ppm镁、小于30ppm硫和小于75ppm硅。
10．按照权利要求1或2的钴金属粉末，其特征在于热压试板上测量，其洛氏硬度至少为98HRB。
11．按照权利要求8的钴金属粉末，其洛氏硬度至少为98HRB(在热压试板上测量)，杂质含量为小于20ppm铝、小于20ppm钙、小于30ppm钠、小于20ppm镁、小于30ppm硫和小于75ppm硅，其BET表面大于0.8m2/g(按氮1-点法(DIN66131)测量)。
12．按照权利要求11的钴金属粉末，其中雾化组分主要是球状的。
CN94112792A 1993-12-21 1994-12-21 钴金属粉末 Expired - Fee Related CN1070094C (zh)

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DE4343594A DE4343594C1 (de) 1993-12-21 1993-12-21 Kobaltmetallpulver sowie daraus hergestellte Verbundsinterkörper
DEP4343594.7 1993-12-21

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EP0659507A1 (de) 1995-06-28
GR3027693T3 (en) 1998-11-30
DE4343594C1 (de) 1995-02-02
RU94045279A (ru) 1997-04-20
KR100340161B1 (ko) 2002-10-31
JPH07207301A (ja) 1995-08-08
CN1112466A (zh) 1995-11-29
KR950017006A (ko) 1995-07-20
RU2126310C1 (ru) 1999-02-20
ATE168054T1 (de) 1998-07-15
EP0659507B1 (de) 1998-07-08
ES2118304T3 (es) 1998-09-16
DE59406412D1 (de) 1998-08-13
US5482530A (en) 1996-01-09
JP3435660B2 (ja) 2003-08-11

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