CN100497699C - High-strength high-ductility thermostable ceramet material - Google Patents
High-strength high-ductility thermostable ceramet material Download PDFInfo
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- CN100497699C CN100497699C CNB2007100348128A CN200710034812A CN100497699C CN 100497699 C CN100497699 C CN 100497699C CN B2007100348128 A CNB2007100348128 A CN B2007100348128A CN 200710034812 A CN200710034812 A CN 200710034812A CN 100497699 C CN100497699 C CN 100497699C
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Abstract
The invention discloses a high-strength high-flexibility thermostable ceramic material, which comprises the following parts: 5%-40% zirconium-corundum, 20%-80% tungsten, 10%-50% chromium, 0.1%-20% cobalt, 1%-20% nickel and 0-15% rare earth, wherein the zirconium-corundum consists of 70%-95% aluminium trioxide and 5%-30% zirconia; the metal ceramic can be sintered through heat pressure and isostatic heat pressure under vacuum.
Description
Technical field
The present invention relates to a kind of material and be particularly related to stupalith, is a kind of cermet material specifically.
Background technology
At present, extruding is an indispensable important means in the metal material processing such as copper, aluminium, and at present the overflow mould used of non-ferrous metal processing industry mainly is two kinds of punching block and cermet molds.What then almost all adopt for the bigger copper alloy of resistance to deformation is that (composition is cermet mold: W, Cr, Ni, Al
2O
3Deng), but from service condition, the existing cermet mold life-span is still unsatisfactory, and situation is more serious when particularly pushing the copper-nickel alloy alloy, and its mean lifetime has only 40～60; On the other hand, the present price is rather stiff of cermet mold.The patent inventor is by studying discovery in great detail, though at present reach requirement as the cermet material hot hardness of ceramic phase with aluminium sesquioxide, but because its toughness is relatively poor, the easy cracking and losing efficacy of hot-extrusion mold in the use, the toughness of therefore improving cermet material is the important channel of improving the sintering metal hot-extrusion mold life-span.
Compare with aluminium sesquioxide,, have high toughness though zirconium dioxide hardness is lower.Zircon corundum (Al
2O
3XZrO
2) be a kind of by corundum (Al
2O
3) and zirconium white (ZrO
2) at high temperature synthetic high-strength and high ductility stupalith more than 2000 ℃, it has the hardness close with aluminium sesquioxide, and toughness improves a lot, can obviously suppress in the stupalith brittle rupture, significantly improve the thermal shock resistance of material; On the other hand, because the wettability of metals such as zirconium white and nickel is better than the wettability of aluminium sesquioxide and metal, therefore contain the zirconium white composition in the ceramic phase and can improve wettability between ceramic phase and the metallographic phase, thereby increase interface bond strength, improve the material monolithic performance.Add La
2O
3, Y
2O
3Deng rare earth oxide to ZrO
2Crystal stability clearly raising effect is arranged, and can further improve the interface bonding state between ceramic phase and the metallographic phase.What of zirconia content have considerable influence to performances such as the stability of zircon corundum, hardness, toughness, anti-thermal shocks in the zircon corundum, and therefore how selecting suitable zircon corundum composition at specific purposes adjustment is that difficult point also is the key of problem.Zircon corundum was mainly used in fire resisting material field in the past, and a small amount of application is also arranged aspect spraying, but did not cause enough attention of people in the application aspect the high-performance metal pottery.
The present invention at the purposes requirement of non-ferrous metal high temperature extrusion mould, by a large amount of tests, proposes to adopt zircon corundum (Al on the basis of fully having studied zircon corundum powdered material character
2O
3XZrO
2) be the ceramic phase raw material, add bonding phase compositions such as W, Cr, Ni, rare earth, prepared high strength, high tenacity, refractory metal stupalith, Performance Detection shows, adopt the die material material of this material manufacturing to have good abrasion resistance and thermal shock resistance, and have very long work-ing life.
Summary of the invention
The objective of the invention is to for solving existing sintering metal hot-extrusion mold material inefficacy easy to crack, short shortcoming of life-span, a kind of cermet material is proposed, this cermet material has high strength, high tenacity and resistant to elevated temperatures characteristics, be applicable to and make hot-extrusion mold, high-temperature structural material, cutting tool etc., can increase substantially intensity, toughness and the resistance to elevated temperatures of above-mentioned materials, increase the service life.
The objective of the invention is to realize by following manner:
Cermet material of the present invention comprises zircon corundum, tungsten, chromium, cobalt, nickel, described zircon corundum accounts for 5～40% of gross weight, described tungsten accounts for 20%-80% of gross weight, described chromium accounts for 10%-50% of gross weight, described cobalt accounts for 0.1%-20% of gross weight, and described nickel accounts for 1%-20% of gross weight.
Cermet material of the present invention also comprises rare earth, and described rare earth accounts for 0-15% of gross weight.
Described zircon corundum is made up of aluminium sesquioxide that accounts for gross weight 70%-95% and the zirconium dioxide that accounts for gross weight 5%-30%.Its size range is: 1-100 μ m.
The preferred weight percent of each composition of cermet material of the present invention is: zircon corundum accounts for 5～30% of gross weight, described tungsten accounts for 30%-55% of gross weight, described chromium accounts for 20%-40% of gross weight, described cobalt accounts for 1%-5% of gross weight, and described nickel accounts for 5%-10% of gross weight.
Cermet material preparation technology of the present invention is: batching, mixing, moulding, sintering, post-treatment; Wherein sintering can adopt following three kinds sintering process: 1. hot pressed sintering: 1600 ℃-1900 ℃ of temperature, sintering time 30-60 minutes, the 1～30MPa that exerts pressure, atmosphere: vacuum or argon gas, nitrogen, hydrogen shield atmosphere.
2. HIP sintering: 1500 ℃-1900 ℃, pressure 50-200Mpa, atmosphere: argon gas, nitrogen, hydrogen shield atmosphere, sintering time 3-8 hour.
3. vacuum presintering+atmosphere sintering: temperature is vacuum atmosphere presintering during by room temperature-1400 ℃, and time 2-4 hour, 1400 ℃-1900 ℃ was sintering under argon gas, nitrogen or the hydrogen shield, time 0.5-3 hour.
Because cermet material of the present invention can solve existing sintering metal hot-extrusion mold material inefficacy easy to crack, short shortcoming of life-span well, have high strength, high tenacity and resistant to elevated temperatures characteristics, corresponding strength, toughness and resistances to elevated temperatures such as the hot-extrusion mold that is obtained by material preparation of the present invention, high-temperature structural material, cutting tool have all obtained promoting significantly, have also prolonged work-ing life.
Embodiment
The present invention is described in detail below by embodiment, following Example just meets several examples of the technology of the present invention content, do not illustrate that the present invention only limits to the described content of following example, the technician in the industry all belongs to content of the present invention according to the product of claim item of the present invention manufacturing.
Embodiment 1
Hot-pressing sintering technique
1) batching: W:147g, Cr:105g, Ni:20g, Co:4g, zircon corundum powder (Al
2O
30.25ZrO
2) (mean particle size 100 μ m): 18g.
2) ball mill mixing: the powder that configures is packed in the Wimet ball milling jar, make ball-milling medium with 100ml ethanol, the ball milling time is 72 hours, behind the ball milling with powder in vacuum in oven dry.
3) hot pressed sintering: the powder sintering in the graphite jig of packing into, sintering carries out in hot-pressed sintering furnace, and sintering temperature is 1800 ℃, sintering time 30 minutes, and the 20MPa that exerts pressure, sintering carries out under argon shield atmosphere.
Prepared material property is as shown in table 1.
Embodiment 2
Hot-pressing sintering technique
1) batching: W:123g, Cr:105g, Ni:20g, Co:4g, La
2O
3: 4g, zircon corundum powder ((Al
2O
30.25ZrO
2)) (mean particle size 150 μ m): 38g.
2) ball mill mixing: with embodiment 1.
3) hot pressed sintering: with embodiment 1.
Prepared material property is as shown in table 1.
Embodiment 3
Hot-pressing sintering technique
1) batching: W:70g, Cr:145g, Ni:5g, Co:0.3g zircon corundum powder ((Al
2O
30.1ZrO
2)) (mean particle size 20 μ m): 80g.
2) ball mill mixing: with embodiment 1.
3) hot pressed sintering: with embodiment 1.
Prepared material property is as shown in table 1.
Embodiment 4
Hot-pressing sintering technique
4) batching: W:100g, Cr:90g, Ni:18g, Co:4g zircon corundum powder (Al
2O
30.1ZrO
2) (mean particle size 20 μ m): 88g.
5) ball mill mixing: with embodiment 1.
6) hot pressed sintering: with embodiment 1.
Prepared material property is as shown in table 1.
Comparative Examples 1
Hot-pressing sintering technique
1) batching: the various raw materials of weighing by weight percentage.W:123g wherein, Cr:105g, Ni:20g, Co:4g, La
2O
3: 4g, white alundum powder (Al
2O
3, mean particle size 150 μ m): 38g.
2) ball mill mixing: with embodiment 1.
3) hot pressed sintering: with embodiment 1.
Prepared material property is as shown in table 1.
Embodiment 5
HIP sintering technology
1) batching: with embodiment 2.
2) ball mill mixing: the powder that configures is packed in the Wimet ball milling jar, add 15g paraffin and make forming agent, make ball-milling medium with 100ml ethanol, the ball milling time is 72 hours, behind the ball milling powder is being dried in vacuum.
3) moulding: the powder steel molding jig is carried out mold pressing earlier, vacuum canning again, cold isostatic compaction then, pressure: 100MPa.
4) come unstuck: be warming up to 680 ℃ gradually by room temperature, the time: 6 hours.
5) HIP sintering: 1600 ℃ of sintering temperatures, pressure 80MPa.
Prepared material property is as shown in table 1.
Embodiment 6
HIP sintering technology
1) batching: the various raw materials of weighing by weight percentage.W:111g wherein, Cr:105g, Ni:20g, Co:4g, La
2O
3: 4g, zircon corundum powder ((Al
2O
30.1ZrO
2)) (mean particle size 20 μ m): 50g.
2) ball mill mixing: with embodiment 1.
3) moulding: with embodiment 4.
4) come unstuck: with embodiment 4.
5) HIP sintering: 1600 ℃ of sintering temperatures, pressure 200MPa.
Prepared material property is as shown in table 1.
Comparative Examples 2
HIP sintering technology
4) batching: the various raw materials of weighing by weight percentage.W:123g wherein, Cr:105g, Nj:20g, Co:4g, La
2O
3: 4g, white alundum powder (Al
2O
3, mean particle size 20 μ m): 50g.
5) ball milling: with embodiment 1.
6) hot pressed sintering: with embodiment 1.
Prepared material property is as shown in table 1.
Embodiment 7
Vacuum presintering+atmosphere sintering technology
1) batching: the various raw materials of weighing by weight percentage.W:123g wherein, Cr:105g, Ni:20g, Co:4g, La
2O
3: 4g, zircon corundum powder ((Al
2O
30.2ZrO
2)) (mean particle size 20 μ m): 38g.
2) ball mill mixing: with embodiment 1.
3) moulding: with embodiment 4.
4) come unstuck: with embodiment 4.
5) vacuum sintering gas-protecting sintering: sintering under 0-1300 ℃ of vacuum atmosphere, 1300 ℃ of insulation logical argon shields after 30 minutes continue to be warming up to 1700 ℃ of insulations 30 minutes.
Prepared material property is as shown in table 1.
Embodiment 8
Vacuum presintering+atmosphere sintering technology
1) batching: the various raw materials of weighing by weight percentage.W:235g wherein, Cr:35g, Ni:14g, Co:1g, zircon corundum powder ((Al
2O
30.2ZrO
2)) (mean particle size 20 μ m): 15g.
2) ball mill mixing: with embodiment 1.
3) moulding: with embodiment 4.
4) come unstuck: with embodiment 4.
5) vacuum sintering gas-protecting sintering: sintering under 0-1300 ℃ of vacuum atmosphere, 1300 ℃ of insulation logical argon shields after 30 minutes continue to be warming up to 1700 ℃ of insulations 30 minutes.
Prepared material property is as shown in table 1.
Embodiment 9
Vacuum presintering+atmosphere sintering technology
1) batching: the various raw materials of weighing by weight percentage.W:80g wherein, Cr:44g, Ni:4g, Co:55g, zircon corundum powder ((Al
2O
30.2ZrO
2)) (mean particle size 20 μ m): 120g.
2) ball mill mixing: with embodiment 1.
3) moulding: with embodiment 4.
4) come unstuck: with embodiment 4.
5) vacuum sintering gas-protecting sintering: sintering under 0-1300 ℃ of vacuum atmosphere, 1300 ℃ of insulation logical argon shields after 30 minutes continue to be warming up to 1700 ℃ of insulations 30 minutes.
Prepared material property is as shown in table 1.
Embodiment 10
Vacuum presintering+atmosphere sintering technology
1) batching: the various raw materials of weighing by weight percentage.W:80g wherein, Cr:44g, Ni:55g, Co:1g, La
2O
3: 40g, zircon corundum powder ((Al
2O
30.2ZrO
2)) (mean particle size 20 μ m): 80g.
2) ball mill mixing: with embodiment 1.
3) moulding: with embodiment 4.
4) come unstuck: with embodiment 4.
5) vacuum sintering gas-protecting sintering: sintering under 0-1300 ℃ of vacuum atmosphere, 1300 ℃ of insulation logical argon shields after 30 minutes continue to be warming up to 1700 ℃ of insulations 30 minutes.
Prepared material property is as shown in table 1.
Comparative Examples 3
Vacuum presintering+atmosphere sintering technology
1) batching: the various raw materials of weighing by weight percentage.W:123g wherein, Cr:105g, Ni:20g, Co:4g, La
2O
3: 4g, white alundum powder (Al
2O
3, mean particle size 20 μ m): 38g.
2) ball milling: with embodiment 1.
3) hot pressed sintering: with embodiment 1.
Prepared material property is as shown in table 1.Table 1: embodiment and Comparative Examples material performance index
Claims (3)
1, a kind of high-strength high-ductility thermostable ceramet material, it is characterized in that: comprise zircon corundum, tungsten, chromium, cobalt, nickel, described zircon corundum accounts for 5～40% of cermet material gross weight, described tungsten accounts for 20%-80% of cermet material gross weight, described chromium accounts for 10%-50% of cermet material gross weight, described cobalt accounts for 0.1%-20% of cermet material gross weight, and described nickel accounts for 1%-20% of cermet material gross weight; Described zircon corundum is made up of aluminium sesquioxide that accounts for zircon corundum gross weight 70%-95% and the zirconium dioxide that accounts for zircon corundum gross weight 5%-30%.
2, a kind of high-strength high-ductility thermostable ceramet material according to claim 1, it is characterized in that: zircon corundum accounts for 5～30% of cermet material gross weight, described tungsten accounts for 30%-55% of cermet material gross weight, described chromium accounts for 20%-40% of cermet material gross weight, described cobalt accounts for 1%-5% of cermet material gross weight, and described nickel accounts for 5%-10% of cermet material gross weight.
3, a kind of high-strength high-ductility thermostable ceramet material according to claim 1 and 2 is characterized in that: also comprise rare earth, described rare earth accounts for 0-15% of gross weight.
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| CN103552099B (en) * | 2013-09-29 | 2015-07-15 | 河南华茂新材料科技开发有限公司 | High-strength ceramic ultrathin cutting blade and production method thereof |
| CN104357725B (en) * | 2014-10-21 | 2016-09-14 | 常熟市金成模具有限公司 | A kind of refractory metal ceramic die material |
| CN105220053A (en) * | 2015-11-14 | 2016-01-06 | 华文蔚 | A kind of heat resistant and wear resistant cermet material and preparation method thereof |
| CN105603284B (en) * | 2016-01-14 | 2017-08-25 | 洛阳三睿宝纳米科技有限公司 | A kind of cermet material of the boehmite containing nanoscale and preparation method thereof |
| JP6717037B2 (en) * | 2016-04-28 | 2020-07-01 | 住友電気工業株式会社 | Alloy powder, sintered body, method for producing alloy powder, and method for producing sintered body |
| CN107034407B (en) * | 2017-05-27 | 2018-07-13 | 遵义中铂硬质合金有限责任公司 | A kind of production method of hard alloy |
| CN108747246A (en) * | 2018-04-27 | 2018-11-06 | 宁夏德运创润钛业有限公司 | A kind of preparation method for squeezing the extrusion die of titanium or titanium alloy tube rod |
| DE102020120189A1 (en) * | 2020-07-30 | 2022-02-03 | Rogers Germany Gmbh | Method for producing a metal-ceramic substrate and a metal-ceramic substrate produced by such a method |
| CN112195385B (en) * | 2020-10-16 | 2021-07-13 | 内蒙金属材料研究所 | High-temperature-resistant high-toughness molybdenum-based composite material and preparation method thereof |
| CN113234950B (en) * | 2021-04-01 | 2022-03-08 | 三峡大学 | Preparation method of Ti (C, N) -based metal ceramic |
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