CN108585870A - A kind of La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials and preparation method thereof - Google Patents
A kind of La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of La2O3‑Al2O3‑(W,Mo2) C non-bond cemented carbides preparation method, include the following steps：Ammonium metatungstate, ammonium molybdate, lanthanum nitrate hexahydrate, nine water aluminum nitrates, glucose are added in deionized water and stirs, continuous heating obtains presoma composite powder until explosive evaporation；Presoma composite powder is placed in airtight tube type stove, after vacuumizing, is passed through H2With N2Mixed gas, be then carbonized, obtain composite granule；Gained composite granule is placed in SPS discharge plasma sintering stoves, at reaction conditions, is prepared into non-bond cemented carbide.Present invention aluminium oxide toughening particle substituted pesticides metallic cobalt, nanometer grade composit powder body is prepared using chemical liquid mixing method, the non-bond cemented carbide of excellent combination property is finally prepared with SPS discharge plasma sintering techniques, and there is more preferably corrosion resistance and deformation resistance, better polishability, higher red hardness.
Description
Technical field
The present invention relates to alloy preparation field, more particularly to a kind of La2O3-Al2O3-(W,Mo2) C non-bond cemented carbides
Material and preparation method thereof.
Background technology
SPS discharge plasma sinterings (Spark Plasma Sintering) are a kind of completely new skills for preparing functional material
Art, energy conservation and environmental protection, institutional framework are controllable, sintering time is shorter and heating rate is its advantage place soon, can be used for preparing pottery
Ceramic material, metal material, composite material are preparing the fields such as amorphous block material, nanometer blocks material, functionally gradient material (FGM) technology
It is widely applied.Japan obtains the patent of spark sintering technology in the sixties in last century, for no other reason than that equipment manufacturing cost,
Industrial production and the sintering relevant technical barrier of efficiency, cause to be not carried out commonly used.It is ground on to the eighties in 19th century well
Study carefully the SPS devices that developed First has 50KN sintering pressures, starts the research applied to Material Field.Nowadays its
Also developmental achievement, the maximum sintering pressure of DC pulse generator have more been up to 100-1000KN to three generations SPS devices,
Industrial requirement is reached.
Ultrafine tungsten carbide (WC) hard alloy has that fracture toughness is preferable, hardness is high and the higher feature of bending resistance, in the modern times
Tool materials, resistant material, wear-resistant material and wear-resistant material etc. have extremely extensive purposes.Metal-processing industry
Technological revolution is precisely due to WC largely replaces caused by high-speed steel, therefore tungsten carbide is known as " industrial tooth
Tooth ".Since cobalt has excellent wet performance to tungsten carbide, and tungsten carbide has certain solubility in cobalt, so always
Since choose bonding agent of the cobalt as composite ceramic material.However, cobalt is a kind of rare, valuable, and the war of great national defence meaning
Slightly resource, China is due to cobalt ore scarcity of resources, and grade is low, position disperses, cost of winning is high.China is used as one at this stage
The quantity of resources consumption big country, annual import cobalt ore is huge, can cause international market resource using external resource in large quantities
The rise of price, at the same time the demand also to domestic causes great price and the market risk, therefore seeks cobalt resource
Substitute reduces cost of alloy, has caused the great interest of vast researcher.
There is scholar to use part metals (Al, Cu, Ni, Fe), intermetallic compound (Fe at present3A, VC, TiC) and oxide
(MgO、ZrO2) etc. already succeeded and certain progress to replace cobalt to prepare tungsten carbide base carbide alloy.Using Fe,
The metals such as Ni replace cobalt, although the similar performance of the mechanical property and WC-Co system hard alloy of the hard alloy prepared,
It is that graphite-phase and carbide easily occur, to be impacted to the performance of material.
Invention content
In order to solve the above technical problem, the present invention provides a kind of good corrosion resistance, deformation resistance is good, better polishability
La good, red hardness is high2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials, and preparation method is provided.
Technical proposal that the invention solves the above-mentioned problems is：A kind of La2O3-Al2O3-(W,Mo2) C non-bond cemented carbides
Material, including following ingredient by mass percentage：Tungsten carbide 81~83%, molybdenum carbide 1.5~3.5%, aluminium oxide 14~
16%, lanthana 0.1~0.3%.
A kind of La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method, include the following steps：
(1) deionized water or distilled water are heated, by ammonium metatungstate, ammonium molybdate, lanthanum nitrate hexahydrate, nine water aluminum nitrates and Portugal
Grape Icing Sugar body, stirring makes it completely dissolved and continuous heating is until deionized water boiling and evaporating completely, obtain carbon containing source distribution
Uniform presoma composite powder.
(2) presoma composite powder obtained by step (1) is placed in airtight tube type stove, after vacuumizing, is passed through H2With N2It is mixed
Gas is closed, is then carbonized, obtains La2O3/Al2O3/(W,Mo2) C composite granules；
(3) composite granule obtained by step (2) is placed in SPS discharge plasma sintering stoves, at reaction conditions, is prepared into
La2O3/Al2O3/(W,Mo2) C non-bond cemented carbides.
Above-mentioned La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method, in the step (1), go
Ionized water or distilled water are heated to 60-70 DEG C.
Above-mentioned La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method, in the step (1), add
Ammonium metatungstate, ammonium molybdate, lanthanum nitrate hexahydrate, nine water aluminum nitrates, the glucose amount entered be respectively 30-32g/L, 0.7-1.6g/L,
0.05-0.3g/L、30-36g/L、16-18g/L。
Above-mentioned La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method, in the step (2), H2
N2In mixed gas, the flow of hydrogen is 0.1~0.2L/min, and the flow of nitrogen is 0.3~0.4L/min.
Above-mentioned La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method, in the step (2), institute
The carburizing temperature stated is 1250 DEG C~1350 DEG C, and the time is 2~3h.
Above-mentioned La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method, in the step (3), institute
The reaction condition stated is：Pulse current ratio is 8-2, and load is 35MPa~45MPa, and temperature is 1500 DEG C~1600 DEG C, room temperature
It is respectively 160 DEG C/min and 80 DEG C/min to the heating rate before 650 DEG C and after 650 DEG C, soaking time is 10~
15min, vacuum degree are maintained at 6Pa.
The beneficial effects of the present invention are：
1, present invention aluminium oxide toughening particle substituted pesticides metallic cobalt is enough using chemical liquid mixing method prepared sizes
Small, the enough pure nanoscale La of powder2O3/Al2O3/(W,Mo2) C composite granules, finally SPS discharge plasma sintering techniques is used to prepare
The La of excellent combination property2O3/Al2O3/(W,Mo2) C non-bond cemented carbides.Compared to traditional hard alloy, soap-free emulsion polymeization
Phase cemented carbide has more preferably corrosion resistance and deformation resistance, better polishability, higher red hardness.
2, in preparation method of the invention, La is prepared by one step carbonization2O3/Al2O3/(W,Mo2) C composite granules, work
Skill is very simple, and condition is easily controllable, and gained composite granule is superfine powder, and average grain diameter is 400~500nm.
3, in preparation method of the invention, by the way that molybdenum element, rare earth billows element is added in technique starting end so that each component
Rationally it is evenly distributed in solution.
4, in preparation method of the invention, glucose starts just to be added thereto in technique so that carbon source and tungstic acid
(WO3) can more be sufficiently mixed, on the one hand the carbon source of W reduction and carbonizations is provided, on the other hand play and inhibit WC in carbonisation
The big effect of grain length.
5, in preparation method of the invention, nine water aluminum nitrates and lanthanum nitrate hexahydrate are just added in solution in technique starting end,
Heating is evaporated obtained aluminium oxide (Al2O3)、La2O3With WO3Uniformly mixed composite granule is mixed with traditional mechanical ball mill
Al2O3、La2O3And WO3Method is compared, and is had introducing impurity few, is uniformly mixed, the advantages such as energy saving.
6, in preparation method of the invention, the sintering time of SPS sintered hard alloys is greatly reduced, and sintering temperature is relatively low,
And effectively inhibit growing up for WC grain.At the same time discharge plasma sintering makes the defects of micropore substantially reduce, and makes product
Comprehensive performance greatly improve.
Description of the drawings
Fig. 1 is 1 gained La of embodiment2O3/Al2O3/(W,Mo2) C composite granules XRD diffraction patterns.
Fig. 2 is 1 gained La of embodiment2O3/Al2O3/(W,Mo2) C composite granules SEM electron-microscope scanning figures.
Fig. 3 is 1 gained La of embodiment2O3/Al2O3/(W,Mo2) C composite granules TEM transmission electron microscope pictures.
Fig. 4 is 1 gained La of embodiment2O3/Al2O3/(W,Mo2) C composite granules EDS energy spectrum analysis figures.
Fig. 5 is 1 gained La of embodiment2O3/Al2O3/(W,Mo2) C non-bond cemented carbides surface SEM microscopic structures photograph
Piece.
Fig. 6 is 1 gained La of embodiment2O3/Al2O3/(W,Mo2) C non-bond cemented carbides fracture apperance figure.
Specific implementation mode
The present invention is further illustrated with reference to the accompanying drawings and examples.
Embodiment 1
1) deionized water 500ml is heated to 60 DEG C；By ammonium metatungstate (NH4)6H2W12O40·XH2O, ammonium molybdate tetrahydrate
H24Mo7N6O24·4H2O, lanthanum nitrate hexahydrate LaN3O9·6H2O, nine water aluminum nitrate Al (NO3)3·9H2O and Dextrose Monohydrate powder
C6H12O6·H2O (each powder purity >=99.5%), addition be respectively 15.29g, 0.75g, 0.04g, 17.63g and
8.69g, stirring make it completely dissolved and continue stirring 0.5 hour, and continuous heating obtains until deionized water boiling and evaporating completely
The La wrapped up to organic carbon source2O3/Al2O3/MoO3/WO3Presoma composite powder.
2) gained presoma composite powder is placed in vacuum tube furnace, is passed through H2/N2Mixed gas, H2And high purity N2's
Gas flow is respectively 0.2L/min and 0.4L/min, and carburizing temperature is 1250 DEG C, soaking time 2h, is carbonized up to nanometer
La2O3/Al2O3/(W,Mo2) C composite granules, powder purity >=99% after testing.
3) by nanometer La2O3/Al2O3/(W,Mo2) C composite granules are placed in SPS discharge plasma sintering stoves, pulse current
Ratio is 8-2, and load 35MPa, temperature is 1500 DEG C, and the heating rate after room temperature to 650 DEG C and 650 DEG C is respectively 160
DEG C/min and 80 DEG C/min, soaking time 10min, vacuum degree is maintained at 6Pa.
Determine obtained La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide each component mass percents be WC81%,
Mo2C2.9%, Al2O316%, La2O30.1%.
The nanometer La that will be obtained2O3/Al2O3/(W,Mo2) C composite granules carry out XRD tests, as shown in Figure 1, can be with from Fig. 1
To find out, the composite powder after carbonization is mainly made of tungsten carbide and aluminium oxide, certainly, also contains minimal amount of lanthana, due to
Content is few, can not detect；The nanometer La that will be obtained2O3/Al2O3/(W,Mo2) C composite granules, under scanning electron microscope and transmission electron microscope
It is as shown in Figures 2 and 3 to carry out microstructure observation, from figures 2 and 3, it will be seen that powder average grain diameter is 400nm；Fig. 4's
EDS energy spectrum analysis detection also shows W elements with C element atomicity percentage composition than being about 1:1, Al element and O Elements Atoms
Number percentage composition is than being about 2:3.By Fig. 5 and Fig. 6 it is found that sintered body micropore is less, consistency is high, crystal grain distribution uniform-dimension
Size reaches 0.6 μm.La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide comprehensive performances are more excellent, average Rockwell hardness >=
HRA94, density can reach 15.2g/cm-3, bending strength 760MPa.
Embodiment 2
1) deionized water 500ml is heated to 65 DEG C；By ammonium metatungstate (NH4)6H2W12O40·XH2O, ammonium molybdate tetrahydrate
H24Mo7N6O24·4H2O, lanthanum nitrate hexahydrate LaN3O9·6H2O, nine water aluminum nitrate Al (NO3)3·9H2O and Dextrose Monohydrate powder
C6H12O6·H2O (each powder purity >=99.5%), addition be respectively 15.66g, 0.39g, 0.12g, 16.76g and
8.65g, stirring make it completely dissolved and continue stirring 1 hour, and continuous heating obtains until deionized water boiling and evaporating completely
The La of carbonaceous sources2O3/Al2O3/MoO3/WO3Presoma composite powder.
2) gained presoma composite powder is placed in vacuum tube furnace, is passed through H2/N2Mixed gas, H2And high purity N2's
Gas flow is respectively 0.1L/min and 0.3L/min, and carburizing temperature is 1350 DEG C, soaking time 2.5h, is carbonized up to nanometer
La2O3/Al2O3/(W,Mo2) C composite granules, powder purity >=99% after testing.
3) by nanometer La2O3/Al2O3/(W,Mo2) C composite granules are placed in SPS discharge plasma sintering stoves, pulse current
Ratio is 8-2, and load 45MPa, temperature is 1600 DEG C, and the heating rate after room temperature to 650 DEG C and 650 DEG C is respectively 160
DEG C/min and 80 DEG C/min, soaking time 15min, vacuum degree is maintained at 6Pa, is prepared into La2O3/Al2O3/(W,Mo2) C is without viscous
Tie phase cemented carbide.
Determine obtained La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide each component mass percents be WC83%,
Mo2C1.5%, Al2O315.2%, La2O30.3%.
Analysis is learnt after testing：Nanometer La made from the present embodiment2O3/Al2O3/(W,Mo2) C composite granules crystallite dimension
It is tiny, average grain diameter 600nm；W elements are with C element atomicity percentage composition than being about 1:1, Al element and O Elements Atoms
Number percentage composition is than being about 2:3.Sintered body micropore is less, and consistency is high, and crystal grain distribution uniform-dimension size reaches 0.8 μm.
La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide comprehensive performances are more excellent, average Rockwell hardness >=HRA92, density can reach
14.5g/cm-3, bending strength 710MPa.
Embodiment 3
1) deionized water 500ml is heated to 70 DEG C；By ammonium metatungstate (NH4)6H2W12O40·XH2O, ammonium molybdate tetrahydrate
H24Mo7N6O24·4H2O, lanthanum nitrate hexahydrate LaN3O9·6H2O, nine water aluminum nitrate Al (NO3)3·9H2O and Dextrose Monohydrate powder
C6H12O6·H2O (each powder purity >=99.5%), addition be respectively 15.53g, 0.91g, 0.08g, 15.43g and
8.92g, stirring make it completely dissolved and continue stirring 0.7 hour, and continuous heating obtains until deionized water boiling and evaporating completely
To the La of carbonaceous sources2O3/Al2O3/MoO3/WO3Presoma composite powder.
2) the presoma composite granule obtained by is passed through H in vacuum tube furnace2/N2Mixed gas, H2And high purity N2's
Gas flow is respectively 0.1L/min and 0.3L/min, and carburizing temperature is 1300 DEG C, soaking time 3h, is carbonized up to nanometer
La2O3/Al2O3/(W,Mo2) C composite granules, powder purity >=99% after testing.
3) by nanometer La2O3/Al2O3/(W,Mo2) C composite granules are placed in SPS discharge plasma sintering stoves, pulse current
Ratio is 8-2, and load 40MPa, temperature is 1550 DEG C, and the heating rate after room temperature to 650 DEG C and 650 DEG C is respectively 160
DEG C/min and 80 DEG C/min, soaking time 13min, vacuum degree is maintained at 6Pa, is prepared into La2O3/Al2O3/(W,Mo2) C is without viscous
Tie phase cemented carbide.
Determine obtained La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide each component mass percents are
WC82.3%, Mo2C3.5%, Al2O314%, La2O30.2%.
Analysis is learnt after testing：Nanometer La made from the present embodiment2O3/Al2O3/(W,Mo2) C composite granules crystallite dimension
It is tiny, average grain diameter 500nm；W elements are with C element atomicity percentage composition than being about 1:1, Al element and O Elements Atoms
Number percentage composition is than being about 2:3.Sintered body micropore is less, and consistency is high, and grain size reaches 0.7 μm.La2O3/
Al2O3/(W,Mo2) C non-bond cemented carbide comprehensive performances are more excellent, average Rockwell hardness >=HRA94, density can reach
14.8g/cm-3, bending strength 740MPa.
Embodiment 4
1) deionized water 500ml is heated to 68 DEG C；By ammonium metatungstate (NH4)6H2W12O40·XH2O, ammonium molybdate tetrahydrate
H24Mo7N6O24·4H2O, lanthanum nitrate hexahydrate LaN3O9·6H2O, nine water aluminum nitrate Al (NO3)3·9H2O and Dextrose Monohydrate powder
C6H12O6·H2O (each powder purity >=99.5%), addition be respectively 15.47g, 0.70g, 0.12g, 16.53g and
8.75g, stirring make it completely dissolved and continue stirring 0.7 hour, and continuous heating obtains until deionized water boiling and evaporating completely
To the La of carbonaceous sources2O3/Al2O3/MoO3/WO3Presoma composite powder.
2) gained presoma composite powder is placed in vacuum tube furnace, is passed through H2/N2Mixed gas, H2And high purity N2's
Gas flow is respectively 0.1L/min and 0.3L/min, and carburizing temperature is 1250 DEG C, soaking time 2.5h, is carbonized up to nanometer
La2O3/Al2O3/(W,Mo2) C composite granules, powder purity >=98% after testing.
3) by nanometer La2O3/Al2O3/(W,Mo2) C composite granules are placed in SPS discharge plasma sintering stoves, pulse current
Ratio is 8-2, and load 37MPa, temperature is 1580 DEG C, and the heating rate after room temperature to 650 DEG C and 650 DEG C is respectively 160
DEG C/min and 80 DEG C/min, soaking time 11min, vacuum degree is maintained at 6Pa, is prepared into La2O3/Al2O3/(W,Mo2) C is without viscous
Tie phase cemented carbide.
Determine La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide each component mass percents be WC82%,
Mo2C2.7%, Al2O315%, La2O30.3%.
Analysis is learnt after testing：Nanometer La made from the present embodiment2O3/Al2O3/(W,Mo2) C composite granules crystallite dimension
It is tiny, average grain diameter 300nm；W elements are with C element atomicity percentage composition than being about 1:1, Al element and O Elements Atoms
Number percentage composition is than being about 2:3.Sintered body micropore is less, and consistency is high, and crystal grain distribution uniform-dimension size reaches 0.6 μm.
La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide comprehensive performances are more excellent, average Rockwell hardness >=HRA95, density can reach
15.1g/cm-3, bending strength 730MPa.
Embodiment 5
1) deionized water 500ml is heated to 68 DEG C；By ammonium metatungstate (NH4)6H2W12O40·XH2O, ammonium molybdate tetrahydrate
H24Mo7N6O24·4H2O, lanthanum nitrate hexahydrate LaN3O9·6H2O, nine water aluminum nitrate Al (NO3)3·9H2O and Dextrose Monohydrate powder
C6H12O6·H2O (each powder purity >=99.5%), addition be respectively 15.66g, 0.62g, 0.04g, 15.98g and
8.80g, stirring make it completely dissolved and continue stirring 0.5 hour, and continuous heating obtains until deionized water boiling and evaporating completely
To the La of carbonaceous sources2O3/Al2O3/MoO3/WO3Presoma composite powder.
2) the presoma composite granule obtained by is passed through H in vacuum tube furnace2/N2Mixed gas, H2And high purity N2's
Gas flow is respectively 0.1L/min and 0.3L/min, and carburizing temperature is 1350 DEG C, soaking time 3h, is carbonized up to nanometer
La2O3/Al2O3/(W,Mo2) C composite granules, powder purity >=98% after testing.
3) by nanometer La2O3/Al2O3/(W,Mo2) C composite granules are placed in SPS discharge plasma sintering stoves, pulse current
Ratio is 8-2, and load 43MPa, temperature is 1530 DEG C, and the heating rate after room temperature to 650 DEG C and 650 DEG C is respectively 160
DEG C/min and 80 DEG C/min, soaking time 15min, vacuum degree is maintained at 6Pa, is prepared into La2O3/Al2O3/(W,Mo2) C is without viscous
Tie phase cemented carbide.
Determine La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide each component mass percents be WC83%,
Mo2C2.4%, Al2O314.5%, La2O30.1%.
Analysis is learnt after testing：Nanometer La made from the present embodiment2O3/Al2O3/(W,Mo2) C composite granules crystal grain distribution
Uniform-dimension is tiny, average grain diameter 700nm；W elements are with C element atomicity percentage composition than being about 1:1, Al element and O
Elements Atom number percentage composition is than being about 2:3.Sintered body micropore is less, and consistency is high, and grain size reaches 0.8 μm.
La2O3/Al2O3/(W,Mo2) C non-bond cemented carbide comprehensive performances are more excellent, average Rockwell hardness >=HRA93, density can reach
14.5g/cm-3, bending strength 750MPa.
Claims (7)
1. a kind of La2O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials, it is characterised in that：Including by mass percentage
The following ingredient of meter：Tungsten carbide 81~83%, molybdenum carbide 1.5~3.5%, aluminium oxide 14~16%, lanthana 0.1~0.3%.
2. a kind of La according to claim 12O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation side
Method, which is characterized in that include the following steps：
(1) deionized water or distilled water are heated, then sequentially adds ammonium metatungstate, ammonium molybdate, lanthanum nitrate hexahydrate, nine water nitric acid
Aluminium, glucose continue agitating and heating until deionized water or distillation boiling water and evaporating completely, obtain before carbon source is evenly distributed
Drive bluk recombination powder；
(2) presoma composite powder obtained by step (1) is placed in airtight tube type stove, after vacuumizing, is passed through H2With N2Gaseous mixture
Then body is carbonized, obtain La2O3/Al2O3/(W,Mo2) C composite granules；
(3) composite granule obtained by step (2) is placed in SPS discharge plasma sintering stoves, at reaction conditions, is prepared into
La2O3/Al2O3/(W,Mo2) C non-bond cemented carbides.
3. La according to claim 22O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method,
It is characterized in that：In the step (1), deionized water or distilled water are heated to 60-70 DEG C.
4. La according to claim 22O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method,
It is characterized in that：In the step (1), ammonium metatungstate, ammonium molybdate, lanthanum nitrate hexahydrate, nine water aluminum nitrates, the glucose amount point of addition
It Wei not 30-32g/L, 0.7-1.6g/L, 0.05-0.3g/L, 30-36g/L, 16-18g/L.
5. La according to claim 22O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method,
It is characterized in that：In the step (2), H2N2In mixed gas, the flow of hydrogen is 0.1~0.2L/min, and the flow of nitrogen is
0.3~0.4L/min.
6. La according to claim 22O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method,
It is characterized in that：In the step (2), the carburizing temperature is 1250 DEG C~1350 DEG C, and the time is 2~3h.
7. La according to claim 22O3-Al2O3-(W,Mo2) C non-bond cemented carbide materials preparation method,
It is characterized in that, in the step (3), the reaction condition is：Pulse current ratio is 8-2, and load is 35MPa~45MPa,
Temperature is 1500 DEG C~1600 DEG C, and room temperature to 650 DEG C of heating rates before and after 650 DEG C is respectively 160 DEG C/min and 80
DEG C/min, soaking time is 10~15min, and vacuum degree is maintained at 6Pa.
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| CN109095471A (en) * | 2018-10-29 | 2018-12-28 | 合肥工业大学 | A kind of preparation method of the WC cladding rare earth oxide non-bond cemented carbide with core-shell structure |
| CN109437908A (en) * | 2018-11-13 | 2019-03-08 | 长沙百川超硬材料工具有限公司 | A kind of high thermohardening hard alloy and preparation method thereof |
| CN112250442A (en) * | 2020-09-30 | 2021-01-22 | 北京科技大学 | Preparation method of high-toughness binderless nanocrystalline hard alloy |
| CN112359241A (en) * | 2020-11-24 | 2021-02-12 | 江西理工大学 | Bicrystal heterogeneous hard alloy and preparation method thereof |
| CN113173789A (en) * | 2021-03-30 | 2021-07-27 | 四川科力特硬质合金股份有限公司 | Non-binding phase corrosion-resistant hard alloy and production process and application thereof |
| CN116969763A (en) * | 2023-09-25 | 2023-10-31 | 成都先进金属材料产业技术研究院股份有限公司 | Graphene-toughened non-bonding-phase WC-based hard alloy and preparation method thereof |
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| CN109095471A (en) * | 2018-10-29 | 2018-12-28 | 合肥工业大学 | A kind of preparation method of the WC cladding rare earth oxide non-bond cemented carbide with core-shell structure |
| CN109437908A (en) * | 2018-11-13 | 2019-03-08 | 长沙百川超硬材料工具有限公司 | A kind of high thermohardening hard alloy and preparation method thereof |
| CN109437908B (en) * | 2018-11-13 | 2021-07-30 | 长沙百川超硬材料工具有限公司 | High-hot-hardness hard alloy and preparation method thereof |
| CN112250442A (en) * | 2020-09-30 | 2021-01-22 | 北京科技大学 | Preparation method of high-toughness binderless nanocrystalline hard alloy |
| CN112250442B (en) * | 2020-09-30 | 2021-08-24 | 北京科技大学 | Preparation method of high-toughness binderless nanocrystalline hard alloy |
| CN112359241A (en) * | 2020-11-24 | 2021-02-12 | 江西理工大学 | Bicrystal heterogeneous hard alloy and preparation method thereof |
| CN113173789A (en) * | 2021-03-30 | 2021-07-27 | 四川科力特硬质合金股份有限公司 | Non-binding phase corrosion-resistant hard alloy and production process and application thereof |
| CN113173789B (en) * | 2021-03-30 | 2023-04-18 | 四川科力特硬质合金股份有限公司 | Non-binding phase corrosion-resistant hard alloy and production process and application thereof |
| CN116969763A (en) * | 2023-09-25 | 2023-10-31 | 成都先进金属材料产业技术研究院股份有限公司 | Graphene-toughened non-bonding-phase WC-based hard alloy and preparation method thereof |
| CN116969763B (en) * | 2023-09-25 | 2023-12-12 | 成都先进金属材料产业技术研究院股份有限公司 | Graphene-toughened non-bonding-phase WC-based hard alloy and preparation method thereof |
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