CN1215091A - 高硬度粉末冶金高速钢件 - Google Patents
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Abstract
一种由粉末冶金法生产的高速钢件,具有高硬度和高的耐磨性的组合,尤其是高温下具有高硬度和高的耐磨性。该复合性质通过复合添加W、Mo、V和Co获得。该钢件尤其适用于制造齿轮切削刀具,例如滚齿刀和表面涂层。
Description
本发明涉及由粉末冶金法生产的高速钢件,其特征在于具有高硬度和高的耐磨性,尤其是高温下的高硬度和高的耐磨性,适用于制造齿轮切削刀具,例如滚齿刀和其它需要非常高的耐磨性的切削用途。
在需要高硬度和高的耐磨性的切削用途中,刀具在使用中要经受超过1000°F的高温,例如会最高达1200°F,通常采用碳化物制造这些刀具。然而,碳化物材料存在明显的缺点,即难以加工到预计的切削加工构型,尤其是复杂的切削表面,并具有韧性较低的特征,从而使碳化物制成的刀具在使用中易于开裂和发生崩裂。在这些用途中,优选使用高速钢,而不是碳化物,因为与碳化物材料相比,高速钢易于加工成预计的切削加工构型,其韧性大大提高了。然而,高速钢尚未在这些用途中使用,因为高速钢在使用传统的碳化物刀具的高温下,不具有必要的高硬度以及高耐磨性。
因此,本发明的目的在于提供一种由粉末冶金法生产的高速钢件,可用于制造齿轮切削刀具,例如滚齿刀和其它需要高耐磨性的切削用途。该材料应能够达到并保持在碳化物切削刀具应用中所预期的高温下的高硬度,而又具有高速钢在韧性和加工性能方面的长处。
本发明大体涉及一种由粉末冶金法生产的压实的高速钢粉末颗粒的高速钢件。该钢基本由以下成分组成:以重量%计,2.4~3.9的碳、0.8以下的锰、0.8以下的硅、3.75~4.75的铬、9.0~11.5的钨、4.75~10.75的钼、4.0~10.0的钒和8.5~16.0的钴以及任选的2.0~4.0的铌,其余为铁和偶存的杂质。
下面是以重量%计,本发明的优选的和更优选的高速钢的组成:
组成 | 合金No.1 | 合金No.2 | 合金No.3 | |||
优选的 | 更优选的 | 优选的 | 更优选的 | 优选的 | 更优选的 | |
C | 2.60-3.50 | 3.00-3.30 | 2.40-3.20 | 2.90-3.10 | 2.90-3.90 | 3.20-3.60 |
Mn | 最大0.8 | 最大0.5 | 最大0.8 | 最大0.5 | 最大0.8 | 最大0.5 |
Si | 最大0.8 | 最大0.5 | 最大0.8 | 最大0.5 | 最大0.8 | 最大0.5 |
Cr | 3.75-4.75 | 4.2-4.6 | 3.75-4.50 | 3.90-4.20 | 3.75-4.50 | 3.90-4.20 |
W | 9.0-11.5 | 10.5-11 | 9.75-10.75 | 10-10.5 | 9.50-11.00 | 10.00-10.50 |
Mo | 9.50-10.75 | 10.00-10.50 | 6.75-8.25 | 7.25-7.75 | 4.75-6.00 | 5.00-5.50 |
V | 4.0-6.0 | 5-5.5 | 5.0-7.0 | 6-6.5 | 8.50-10.00 | 9.00-9.50 |
Nb | 2.0-4.0 | 2.8-3.2 | - | - | - | - |
Co | 14.00-16.00 | 14.50-15.00 | 13.00-15.00 | 14-14.5 | 8.50-10.00 | 9.00-9.50 |
根据本发明的钢件在淬火和回火后,可具有70Rc的最小硬度,优选在1200°F回火后具有61Rc的最小硬度。优选地,钢件在淬火和回火后,具有72Rc的最小硬度。而在1200°F回火后优选具有63Rc的硬度。
本发明的钢件可具有齿轮切削刀具,例如滚齿刀,或者在基体上的表面涂层的形式。
图1是显示本发明合金与传统粉末冶金法生产的合金的回火响应性对比图;
图2是显示本发明合金与传统粉末冶金法生产的合金的高温硬度对比图;
通过实施本发明,根据表1所示的合金组成,以重量%计,制备了用于试验的粉末冶金法生产的钢件。
表1 | |||||||||||||||
合金 | C | Mn | Si | Cr | W | Mo | V | Nb | Co | Ti | Al | P | S | O | N |
Rex 76 | 1.52 | 0.32 | 0.32 | 3.79 | 9.72 | 5.31 | 3.14 | - | 8.22 | - | - | 0.015 | 0.059 | 0.009 | 0.031 |
Rex 25 | 1.78 | 0.33 | 0.43 | 3.94 | 12.6 | 6.52 | 5.1 | 0.02 | 0.34 | 0.004 | - | 0.017 | 0.062 | - | 0.046 |
M25a | 1.93 | 0.33 | 0.43 | 3.94 | 12.6 | 6.52 | 5.1 | 0.02 | 0.34 | 0.004 | - | 0.017 | 0.062 | - | 0.046 |
M25b | 2.03 | 0.33 | 0.43 | 3.94 | 12.6 | 6.52 | 5.1 | 0.02 | 0.34 | 0.004 | - | 0.017 | 0.062 | - | 0.046 |
M2511a | 1.89 | 0.26 | 0.76 | 4.2 | 11.91 | 10.95 | 5.01 | - | - | - | - | - | - | 0.005 | 0.03 |
M2511b | 2.19 | 0.26 | 0.76 | 4.2 | 11.91 | 10.95 | 5.01 | - | - | - | - | - | - | 0.005 | 0.03 |
M2511c | 2.34 | 0.26 | 0.76 | 4.2 | 11.91 | 10.95 | 5.01 | - | - | - | - | - | - | 0.005 | 0.03 |
M2511d | 2.44 | 0.26 | 0.76 | 4.2 | 11.91 | 10.95 | 5.01 | - | - | - | - | - | - | 0.005 | 0.03 |
M766a | 2.23 | 0.47 | 0.38 | 3.88 | 10.01 | 5.1 | 6.07 | - | 9.11 | - | - | 0.01 | 0.006 | 0.029 | 0.05 |
M766b | 2.33 | 0.47 | 0.38 | 3.88 | 10.01 | 5.1 | 6.07 | - | 9.11 | - | - | 0.01 | 0.006 | 0.029 | 0.05 |
M766c | 2.53 | 0.47 | 0.38 | 3.88 | 10.01 | 5.1 | 6.07 | - | 9.11 | - | - | 0.01 | 0.006 | 0.029 | 0.05 |
M769a | 2.97 | 0.47 | 0.35 | 3.94 | 10.19 | 5.2 | 9.12 | - | 9.17 | - | - | 0.01 | 0.005 | 0.011 | 0.039 |
M769b | 3.12 | 0.47 | 0.35 | 3.94 | 10.19 | 5.2 | 9.12 | - | 9.17 | - | - | 0.01 | 0.005 | 0.011 | 0.039 |
E1a | 2.24 | 0.42 | 0.50 | 3.96 | 12.15 | 6.75 | 5.04 | 2.59 | 5.99 | - | - | 0.01 | 0.004 | 0.009 | 0.041 |
E1b | 2.39 | 0.42 | 0.50 | 3.96 | 12.15 | 6.75 | 5.04 | 2.59 | 5.99 | - | - | 0.01 | 0.004 | 0.009 | 0.041 |
E2a | 1.80 | 0.42 | 0.51 | 4.04 | 6.11 | 9.86 | 3.07 | 1.97 | 11.96 | - | 0.52 | 0.01 | 0.006 | 0.009 | 0.021 |
E2b | 1.95 | 0.42 | 0.51 | 4.04 | 6.11 | 9.86 | 3.07 | 1.97 | 11.96 | - | 0.52 | 0.01 | 0.006 | 0.009 | 0.021 |
E3a | 2.19 | 0.42 | 0.51 | 3.98 | 4.96 | 10.10 | 4.90 | 2.53 | 7.83 | - | - | 0.01 | 0.005 | 0.008 | 0.042 |
E3b | 2.34 | 0.42 | 0.51 | 3.98 | 4.96 | 10.10 | 4.90 | 2.53 | 7.83 | - | - | 0.01 | 0.005 | 0.008 | 0.042 |
E4a | 2.34 | 0.42 | 0.50 | 4.00 | 5.00 | 10.22 | 4.01 | 2.45 | 7.85 | 0.51 | 0.71 | 0.01 | 0.005 | 0.009 | 0.044 |
E4b | 2.39 | 0.42 | 0.50 | 4.00 | 5.00 | 10.22 | 4.01 | 2.45 | 7.85 | 0.51 | 0.71 | 0.01 | 0.005 | 0.009 | 0.044 |
E6a | 3.04 | 0.58 | 0.67 | 4.00 | 10.04 | 6.00 | 9.98 | - | 17.81 | - | - | 0.01 | 0.011 | 0.01 | 0.035 |
E6b | 3.54 | 0.58 | 0.67 | 4.00 | 10.04 | 6.00 | 9.98 | - | 17.81 | - | - | 0.01 | 0.011 | 0.01 | 0.035 |
E7 | 2.46 | 0.56 | 0.56 | 4.04 | 9.06 | 10.11 | 4.47 | 2.50 | 14.69 | - | - | 0.01 | 0.013 | 0.008 | 0.017 |
A1a | 2.66 | 0.56 | 0.56 | 4.04 | 9.06 | 10.11 | 4.47 | 2.50 | 14.69 | - | - | 0.01 | 0.013 | 0.008 | 0.017 |
A1b | 2.96 | 0.56 | 0.56 | 4.04 | 9.06 | 10.11 | 4.47 | 2.50 | 14.69 | - | - | 0.01 | 0.013 | 0.008 | 0.017 |
A1c | 3.02 | 0.44 | 0.44 | 4.41 | 10.99 | 10.2 | 5.22 | 3.08 | 14.96 | - | - | 0.016 | 0.014 | 0.01 | 0.021 |
A1d | 3.27 | 0.44 | 0.44 | 4.41 | 10.99 | 10.2 | 5.22 | 3.08 | 14.96 | - | - | 0.016 | 0.014 | 0.01 | 0.021 |
A2a | 2.44 | 0.58 | 0.54 | 3.90 | 10.05 | 7.59 | 5.31 | - | 13.97 | - | - | 0.01 | 0.011 | 0.009 | 0.017 |
A2b | 2.59 | 0.58 | 0.54 | 3.90 | 10.05 | 7.59 | 5.31 | - | 13.97 | - | - | 0.01 | 0.011 | 0.009 | 0.017 |
A2c | 2.74 | 0.58 | 0.54 | 3.90 | 10.05 | 7.59 | 5.31 | - | 13.97 | - | - | 0.01 | 0.011 | 0.009 | 0.017 |
A2d | 2.82 | 0.43 | 0.42 | 3.98 | 10.43 | 7.44 | 6.35 | - | 14.15 | - | - | 0.008 | 0.012 | 0.011 | 0.024 |
A2e | 3.07 | 0.43 | 0.42 | 3.98 | 10.43 | 7.44 | 6.35 | - | 14.15 | - | - | 0.008 | 0.012 | 0.011 | 0.024 |
A3a | 3.37 | 0.47 | 0.35 | 3.94 | 10.19 | 5.2 | 9.12 | - | 9.17 | - | - | 0.01 | 0.005 | 0.011 | 0.039 |
A3b | 3.47 | 0.47 | 0.35 | 3.94 | 10.19 | 5.2 | 9.12 | - | 9.17 | - | - | 0.01 | 0.005 | 0.011 | 0.039 |
A3c | 3.57 | 0.47 | 0.35 | 3.94 | 10.19 | 5.2 | 9.12 | - | 9.17 | - | - | 0.01 | 0.005 | 0.011 | 0.039 |
组成由表1所示的用于试验的钢件,采用传统的粉末冶金法生产,包括通过氮气雾化生产预合金粉末,并随后利用热等静压达到完全致密化。
对表1中的试样进行奥氏体化,油淬,并且回火四次,每次两小时,热处理温度如表2所示。对这些试样随后进行试验,测量在上述温度下回火后的硬度。如表3所示,采用销式磨损试验和交叉圆柱试验测定了耐磨性。沿纵向和横向测定了采用表3中所示淬火和回火温度热处理后的试样的弯曲破坏强度和夏氏C型缺口冲击韧性。
表2:可能用于超硬用途的合金的回火响应性 | ||||||||
合金 | 回火响应性*-硬度Rc | |||||||
臭氏体化°F | 950°F | 1000°F | 1025°F | 1050°F | 1100°F | 1150°F | 1200°F | |
Rex 76 | 2200 | 66.9 | 68.9 | - | 66.5 | 65.9 | - | 57.0 |
Rex 25 | 2250 | 67.8 | 67.8 | - | 66.1 | 64.4 | - | 55.7 |
M25a | 2225 | 68.4 | 68.5 | - | 66.7 | 65.2 | - | 56.6 |
M25b | 2225 | 67.4 | 68.4 | - | 67.8 | 65.7 | - | 57.2 |
M2511a | 2250 | 69.1 | 68.8 | 68.1 | - | - | 63.2 | - |
M2511b | 2250 | 66.7 | 69.2 | 69.7 | - | - | 66.4 | - |
M2511c | 2225 | 65.7 | 68.6 | 69.2 | - | - | 66.6 | - |
M2511d | 2225 | 64.2 | 67.5 | 68.7 | - | - | 65.3 | - |
M766a | 2200 | 70.0 | 70.2 | - | 68.7 | 66.8 | - | 57.1 |
M766b | 2200 | 69.7 | 70.1 | - | 69.2 | 67.5 | - | 58.2 |
M766c | 2175 | 69.3 | 69.8 | - | - | - | - | - |
M769a | 2200 | 70.2 | 69.8 | - | 67.9 | 66.4 | - | 56.2 |
M769b | 2175 | 70.2 | 70.0 | - | - | - | - | - |
E1a | 2200 | 69.3 | 68.2 | - | 67.2 | 62.2 | - | 52.4 |
E1b | 2200 | 69.3 | 69.4 | - | 67.4 | 62.9 | - | 55.8 |
E2b | 2200 | 70.4 | 69.8 | - | 68.1 | 63.9 | - | 55.6 |
E3a | 2200 | 68.9 | 67.5 | - | 65.4 | 61.4 | - | 53.9 |
E3b | 2200 | 69.2 | 68.2 | - | 66.4 | 64.9 | - | 53.9 |
E4a | 2200 | 69.1 | 68.9 | - | 67.6 | 62.2 | - | 54.9 |
E4b | 2200 | 69.0 | 69.9 | - | 67.2 | 63.9 | - | 55.0 |
E6a | 2225 | 70.1 | 68.9 | - | 67.8 | 66.1 | - | 60.6 |
E6b | 2225 | 71.7 | 70.7 | - | 69.5 | 67.1 | - | 59.3 |
E7 | 2225 | 72.2 | 70.3 | - | 70.4 | 67.6 | - | 57.5 |
A1a | 2240 | 71.7 | 72.3 | - | 70.8 | 68.9 | - | 62.5 |
A1b | 2225 | 68.9 | 71.3 | - | 71.1 | 70.0 | - | 63.8 |
A1c | 2200 | 70.3 | 72.6 | - | 72.2 | 70.9 | - | 63.1 |
A1d | 2200 | 70 | 72.3 | - | 72.6 | 70.9 | - | 63.8 |
A2a | 2225 | 71.8 | 71.0 | - | 70.8 | 68.5 | - | 60.9 |
A2b | 2200 | 69.5 | 71.4 | - | 71.0 | 68.8 | - | 60.3 |
A2C | 2200 | 67.5 | 70.9 | - | 70.6 | 68.8 | - | 60.3 |
A2d | 2200 | 69.2 | 71.6 | - | 70.8 | 69.9 | - | 62.3 |
A2e | 2200 | 69.4 | 71.4 | - | 71.4 | 69.3 | - | 62.6 |
A3a | 2240 | 67.7 | 71.2 | - | 69.6 | 68.5 | - | 62.5 |
A3b | 2240 | 66.2 | 69.2 | - | 70.2 | 68.9 | - | 62.5 |
A3c | 2240 | 68.7 | 70.2 | - | 70.0 | 68.1 | - | 62.6 |
*在指定温度回火4×2小时后的硬度 |
表3:用于极高硬度场合的选定合金的夏氏C型缺口冲击能量,弯曲破坏强度和耐磨性 | |||||||
合金 | 热处理温度奥氏体化/回火(°F/°F) | C型缺口能量(ft.lbs.) | 弯曲破坏强度(ksi) | 销式磨损试验(mg) | 交叉圆柱试验1010psi | ||
纵向 | 横向 | 纵向 | 横向 | ||||
REX 76 | 2175/1025 | 11 | 6.5 | 576 | 390 | 38.3 | 42 |
REX 25 | 2250/1025 | 9.5 | 531 | ||||
E6a | 2250/1025 | 4.7 | 3.7 | 360 | 300 | ||
E6b | 2240/1025 | 2.7 | 2.2 | 253 | 228 | 9.3 | 104 |
E7 | 2225/1025 | 3.8 | 3.5 | 321 | 154 | 15 | 71 |
A1c | 2200/1025 | 1.7 | 1.6 | 196 | 158.0 | 2.2 | 73 |
A2a | 2200/1025 | 2.6 | 2.6 | 294 | 218 | 4.9 | 77 |
A2d | 2200/1025 | 2.0 | 1.7 | 219 | 163 | 2.9 | 81 |
A3a | 2225/1025 | 3.8 | 3.3 | 292 | 231 | 2.1 | 102 |
合金A1a~A1d、A2a~A2e和A3a~A3c都是根据本发明的组成的合金。如表2中所示和图解表示于图1中的回火响应性数据,与现有的工业合金相比,本发明的A1、A2和A3系列合金在最高达1200°F的回火温度下表现出优异的硬度。类似地,如表3所示,本发明的试样A1c、A2a、A2d和A3a也表现出极好的耐磨性,耐磨性采用销式磨损试验和交叉圆柱试验测定。本发明的这些合金中,合金A1显示对回火响应性和耐磨性的最佳组合。合金A2显示在1200°F回火后硬度稍低,但是与合金A1相比,在一定程度上提高了韧性和弯曲破坏强度。然而,如表3和图1中所示,与现有工业合金相比,所有本发明的合金都表现出综合改善了的回火响应性、韧性和耐磨性。
表4 CPM Rex 76和新合金的高温硬度(HRC) | ||||||||
合金 | 试验温度(°F) | |||||||
75 | 950 | 1000 | 1050 | 1100 | 1150 | 1200 | 1300 | |
REX 76 | 67.5 | 60 | 59.5 | 59 | 58 | 52.5 | 46.5 | - |
A1c | 73.5 | - | 64.5 | - | 63 | - | 57.5 | 39 |
A2d | 72 | - | 63 | - | 60 | - | 56 | 38.5 |
A2e | 72 | - | 62.5 | - | 60 | - | 56 | 39 |
A3a | 71.5 | - | 61 | - | 58.5 | - | 53 | 33.5 |
表4和图2显示了与现有工业合金(REX76)相比,本发明的合金A1c、A2d、A2c和A3a的高温硬度值。从该数据可见,与现有工业合金相比,在最高达1300°F的高温下,所有本发明合金都表现出更高的高温硬度值。
除非另作说明,在本说明书中出现的组成均以重量%计。
Claims (15)
1.一种由粉末冶金法生产的压实的高速钢粉末颗粒的高速钢件,该钢的基本组成如下:以重量%计,2.4~3.9的碳、0.8以下的锰、0.8以下的硅、3.75~4.75的铬、9.0~11.5的钨、4.75~10.75的钼、4.0~10.0的钒和8.5~16.0的钴以及任选的2.0~4.0的铌,其余为铁和偶存的杂质。
2.根据权利要求1的钢件,该钢件含有2.6~3.5的碳、3.75~4.75的铬、9.0~11.5的钨、9.5~10.75的钼、4.0~6.0的钒、2~4的铌和14.0~16.0的钴。
3.根据权利要求2的钢件,该钢件含有3.0~3.3的碳、0.5以下的锰、0.5以下的硅、4.2~4.6的铬、10.5~11.0的钨、10.0~10.5的钼、5.0~5.5的钒、2.8~3.2的铌和14.5~15.0的钴。
4.根据权利要求1的钢件,该钢件含有2.4~3.2的碳、3.75~4.5的铬、9.75~10.75的钨、6.75~8.25的钼、5.0~7.0的钒和13.0~15.0的钴。
5.根据权利要求4的钢件,该钢件含有2.9~3.10的碳、0.5以下的锰、0.5以下的硅、3.9~4.2的铬、10.0~10.5的钨、7.25~7.75的钼、6.0~6.5的钒和14.0~14.5的钴。
6.根据权利要求1的钢件,该钢件含有2.9~3.9的碳、3.75~4.5的铬、9.5~11.0的钨、4.75~6.0的钼、8.5~10.0的钒和8.5~10.0的钴。
7.根据权利要求6的钢件,该钢件含有3.2~3.6的碳、0.5以下的锰、0.5以下的硅、3.9~4.2的铬、10.0~10.5的钨、5~5.5的钼、9.0~9.5的钒和9.0~9.5的钴。
8.根据权利要求1、2、3、4、5、6或者7的钢件,该钢件在淬火和回火条件下,具有70Rc的最低硬度。
9.根据权利要求1、2、3、4、5、6、7或者8的钢件,该钢件在刚淬火后具有70Rc的最低硬度,在1200°F回火后具有61Rc的最低硬度。
10.根据权利要求8的钢件,其中,所述最低硬度是72Rc。
11.根据权利要求9的钢件,其中,所述在1200°F回火后的最低硬度是63Rc。
12.根据权利要求8的钢件,该钢件具有齿轮切削刀具形式。
13.根据权利要求9的钢件,该钢件具有齿轮切削刀具形式。
14.根据权利要求8的钢件,该钢件具有基体上的表面涂层形式。
15.根据权利要求9的钢件,该钢件具有基体上的表面涂层形式。
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US949,497 | 1997-10-14 | ||
US08/949,497 US6057045A (en) | 1997-10-14 | 1997-10-14 | High-speed steel article |
US949497 | 1997-10-14 |
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HK (1) | HK1019621A1 (zh) |
HU (1) | HU220123B (zh) |
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PL (1) | PL190146B1 (zh) |
PT (1) | PT909829E (zh) |
SG (1) | SG72875A1 (zh) |
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- 1998-10-06 CZ CZ0322498A patent/CZ297201B6/cs not_active IP Right Cessation
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- 1998-10-09 JP JP28787498A patent/JP3759323B2/ja not_active Expired - Lifetime
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- 1998-10-13 EP EP98308340A patent/EP0909829B1/en not_active Expired - Lifetime
- 1998-10-13 DE DE69823951T patent/DE69823951T2/de not_active Expired - Lifetime
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- 1998-10-14 KR KR1019980043073A patent/KR19990037098A/ko not_active Application Discontinuation
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- 1998-10-14 CN CN98121315A patent/CN1087358C/zh not_active Expired - Lifetime
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CN1293967C (zh) * | 2002-03-01 | 2007-01-10 | 普莱克斯S.T.技术有限公司 | 抗腐蚀的粉末和涂层 |
CN103572170A (zh) * | 2013-10-28 | 2014-02-12 | 任静儿 | 一种粉末冶金割草机用工具钢 |
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CN104708005B (zh) * | 2013-12-12 | 2017-10-03 | 百乐特殊钢有限两合公司 | 制造能沉淀硬化合金的物品或工具的半成品及其制造方法 |
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CN111136276A (zh) * | 2019-12-12 | 2020-05-12 | 北京机科国创轻量化科学研究院有限公司 | 一种高速钢刀具的制备方法 |
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HUP9802355A2 (hu) | 1999-06-28 |
TW430578B (en) | 2001-04-21 |
CZ297201B6 (cs) | 2006-09-13 |
EP0909829A2 (en) | 1999-04-21 |
AR017335A1 (es) | 2001-09-05 |
CA2249881C (en) | 2007-08-07 |
HUP9802355A3 (en) | 2001-01-29 |
CZ322498A3 (cs) | 1999-08-11 |
CN1087358C (zh) | 2002-07-10 |
PL190146B1 (pl) | 2005-11-30 |
ATE267272T1 (de) | 2004-06-15 |
EP0909829B1 (en) | 2004-05-19 |
CA2249881A1 (en) | 1999-04-14 |
PT909829E (pt) | 2004-09-30 |
DE69823951D1 (de) | 2004-06-24 |
TR199802063A2 (xx) | 1999-05-21 |
BR9803901A (pt) | 1999-12-21 |
EP0909829A3 (en) | 2002-07-10 |
SK284077B6 (sk) | 2004-09-08 |
HK1019621A1 (en) | 2000-02-18 |
SG72875A1 (en) | 2000-05-23 |
MY115612A (en) | 2003-07-31 |
DE69823951T2 (de) | 2005-05-19 |
ES2221126T3 (es) | 2004-12-16 |
JP3759323B2 (ja) | 2006-03-22 |
TR199802063A3 (tr) | 1999-05-21 |
HU9802355D0 (en) | 1998-12-28 |
KR19990037098A (ko) | 1999-05-25 |
SK140498A3 (en) | 1999-06-11 |
HU220123B (hu) | 2001-11-28 |
PL329185A1 (en) | 1999-04-26 |
JPH11189852A (ja) | 1999-07-13 |
US6057045A (en) | 2000-05-02 |
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