CN104451321B - A kind of tungsten carbide niobium zirconium solid solution powder and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of solid-solution powder, particularly a kind of tungsten carbide niobium zirconium solid solution powder, belongs to Hardmetal materials Material Field. The present invention, for reducing Hardmetal materials cost, provides a kind of tungsten carbide niobium zirconium solid solution powder, and the chemical formula of described tungsten carbide niobium zirconium solid solution is (W_0.17-0.21Ti_0.24-0.29Nb_0.31-0.36Zr_0.19-0.22) C; The present invention also provides the preparation method of described tungsten carbide niobium zirconium solid solution powder. The tungsten carbide niobium zirconium solid solution powder that the present invention obtains uses NbC and ZrC combination to replace TaC can obtain function admirable and solid-solution powder with low cost, for hard alloy cutter, can improve well the cutting ability of cutter.

Description

A kind of tungsten carbide niobium zirconium solid solution powder and preparation method thereof

Technical field

The present invention relates to a kind of solid-solution powder, particularly a kind of tungsten carbide niobium zirconium solid solution powder, belongs to hardAlloy material Material Field.

Background technology

Cemented carbide cutting tool is improving constantly and cutting speed due to processed material hardness in the time of cutting steelRaising, the high-temperature behavior of alloy is also had higher requirement. In prior art, normally add (Ta, Nb) C to hardIn matter alloy blade, one of its effect: as carbide alloy grain growth inhibitor, can stop hard after interpolation (Ta, Nb) CIn matter alloy sintering process, crystal grain grows up; Two of its effect, be form together with TiC except WC and Co the 3rd moreLoose phase, significantly increases the heat shock resistance of carbide alloy, and heat resistanceheat resistant is pressed and oxidation resistant ability and improve the red hardness of carbide alloy.

In order to improve the physical and mechanical property of carbide alloy, often add the compound solid solution of WC-TiC-TaC, hard to improveThe cutting ability of matter alloy. In recent years along with the soaring of TaC price, scientific research personnel all find novel without Ta solid solution, withReduce the cost of Hardmetal materials, can have application widely.

Summary of the invention

The technical problem that the present invention solves is to utilize without Ta solid solution and realize the order that reduces Hardmetal materials cost.

One of technical scheme of the present invention is to provide a kind of tungsten carbide niobium zirconium solid solution powder, described tungsten carbide niobiumThe chemical formula of zirconium solid solution is (W_0.17-0.21Ti_0.24-0.29Nb_0.31-0.36Zr_0.19-0.22）C。

Further, the chemical formula of described tungsten carbide niobium zirconium solid solution is (W_0.20Ti_0.24Nb_0.35Zr_0.21）C。

Further, the chemical formula of described tungsten carbide niobium zirconium solid solution is (W_0.20Ti_0.28Nb_0.32Zr_0.20）C。

Further, the chemical formula of described tungsten carbide niobium zirconium solid solution is (W_0.17Ti_0.26Nb_0.36Zr_0.21）C。

Two of technical scheme of the present invention is, the method for the described tungsten carbide niobium zirconium solid solution powder of preparation is provided, and comprisesFollowing steps:

1) take respectively by weight 30～35 parts of WC, 30～35 parts of NbC, 17～22 parts of ZrC, 15～20 parts of TiO₂And7～9 parts of hydrocarbon black powders, are mixed to get raw mixture;

2), using alcohol as ball-milling medium, obtain raw mixture slip by rolling ball milling;

3) described raw mixture slip is dry, then wipe sieve, drum polletizing, obtain compound;

4) described compound is reacted to 2～4h under 1700～1900 DEG C of conditions, obtain tungsten carbide niobium zirconium solid solutionPowder.

Further, step 2) in add the polyethylene glycol of raw mixture quality 2～5%.

Further, in step 3), dry condition is-0.02～-0.08MPa, 70～80 DEG C.

Further, described compound granularity is about 0.5～1mm.

The present invention is with TiO₂As Ti source, respectively using WC as W source, ZrC is as Zr source, and NbC is as Nb source, then is equipped withA certain amount of carbon black reduction TiO₂, under vacuum, carry out solid solution reaction, thereby make solid-solution powder.

The NbC using in the present invention replaces TaC, and high temperature hardness (being red hardness), the high temperature that can improve equally alloy are strongDegree and non-oxidizability, generally, the mass fraction of TaC in alloy is 2%-10%, and NbC is crisp compared with TaC, and general addition existsMass fraction in alloy is 2%-5%. ZrC, as a kind of metal carbides of infusibility, has high-melting-point, high rigidity, high thermal conductanceWith good characteristics such as electrical conductivity and high chemical stabilities. The present invention also adds ZrC, and NbC and ZrC match and can improveThe toughness of material, finally makes alloy material cutting serviceability to improve. Product of the present invention can not only ensure that alloy property reachesTo adding the effect that Ta is the same, the more important thing is and can significantly reduce costs (approximately 2500 yuan/kilogram of TaC, approximately 800 yuan/public affairs of NbC, ZrCJin).

The present invention utilizes ethanol as ball-milling medium, and the powder that it can make various proportion differ greatly mixes (as WC powderWith C powder); Adding PEG is surfactant, and it can change the charge condition of powder surface, is beneficial to below dry, driedPowder does not become lumps.

Described solid-solution powder provided by the invention can improve the high-temperature behavior of carbide alloy. The solid-solution powder tool of gainedHaving good solid solubility, is phase structure by XRD analysis, and the purity of product is high simultaneously, and oxygen content is low.

The invention has the beneficial effects as follows, use NbC and ZrC combination to replace TaC can obtain function admirable and with low costSolid-solution powder, for hard alloy cutter, can improve the cutting ability of cutter well.

Brief description of the drawings

Fig. 1 is the XRD collection of illustrative plates of WTNZ1 in embodiment 1.

Fig. 2 is the XRD collection of illustrative plates of WTNZ2 in embodiment 2.

Fig. 3 is the XRD collection of illustrative plates of WTNZ3 in embodiment 3.

Detailed description of the invention

Below in conjunction with embodiment, the invention will be further described.

Embodiment 1

Adopting granularity is the TiO of 1.0 μ m₂Powder, 2 μ mWC, ZrC and NbC and hydrocarbon black powder be as raw material, itsQuality proportioning is TiO₂: WC:ZrC:NbC:C=17:32:19:32:7.66. In batch mixing process, add and be about mixed raw material weightThe PEG-4000 of amount 3% is as surfactant. Be-0.04MPa by the slip mixing in vacuum, temperature is 78 DEG CDry under condition, material to be mixed takes out after being down to room temperature, sieves and drum polletizing, and making granularity is 0.8mm particle powderEnd, then by particle powder at 1900 DEG C of temperature, in vacuum carbon tube furnace, vacuum solid solution 2.5 hours, is finally organized as（W_0.20Ti_0.24Nb_0.35Zr_0.21) the WTNZ1 solid-solution powder of C.

The performance indications of powder:

1) prepared powder is face-centered cubic crystal formation product, and several compounds have reached good solid solution, and Fig. 1 has shownThe XRD collection of illustrative plates of prepared solid-solution powder WTNZ1;

2) particle mean size of prepared powder is 1.5-2.0 μ m;

3) WTNZ1 solid solution chemical composition table 1

Table 1WTNZ1 chemical composition

Element	W%	Ti%	Nb%	Zr%	CT%	CF%	O%	N%
									Test value	31.25	10.74	29.50	17.70	10.41	0.18	0.15	0.17

Obtained powder composition conforms to design load substantially as can be seen from the above table, and oxygen content is very low≤and 0.20%, powder toolThere is higher purity (> 99%).

Embodiment 2

Adopting granularity is the TiO of 1.0 μ m₂Powder, 2 μ mWC, ZrC and NbC hydrocarbon black powder be as raw material, its qualityProportioning is TiO₂: the hydrocarbon black powder of WC:ZrC:NbC=20:35:18:30:9. In batch mixing process, add and be about mixed raw materialThe PEG-4000 of weight 2% is as surfactant. Be-0.04Mpa that temperature is 70 DEG C by the slip mixing in vacuumCondition under dry, material to be mixed takes out after being down to room temperature, sieves and drum polletizing, making granularity is 1.0mm particle powderEnd, then by particle powder at 1800 DEG C of temperature, in vacuum tank, vacuum solid solution 4 hours, is finally organized as (W_0.20Ti_0.28Nb_0.32Zr_0.20) the WTNZ2 solid-solution powder of C.

The performance indications of powder:

1) prepared powder is face-centered cubic crystal formation product, and several compounds have reached good solid solution, and Fig. 2 has shownThe XRD collection of illustrative plates of prepared solid-solution powder WTNZ2;

2) particle mean size of prepared powder is 1.5-2.0 μ m;

3) WTNZ2 solid solution chemical composition table 2

Table 2WTNZ2 chemical composition

Element	W%	Ti%	Nb%	Zr%	CT%	CF%	O%	N%
									Test value	33.51	12.0	27.09	16.20	10.52	0.18	0.18	0.16

Obtained powder composition conforms to design load substantially as can be seen from the above table, and oxygen content is very low≤and 0.20%, powder toolThere is higher purity (> 99%).

Embodiment 3

Adopting granularity is the TiO of 1.0 μ m₂Powder, 2 μ mWC, ZrC and NbC hydrocarbon black powder are as raw material, and its quality is joinedThan being TiO₂: the hydrocarbon black powder of WC:ZrC:NbC=18:30:19:33:8 part. In batch mixing process, add and be about mixed raw materialThe PEG-4000 of weight 5% is as surfactant. Be-0.05MPa that temperature is 80 DEG C by the slip mixing in vacuumCondition under dry, material to be mixed takes out after being down to room temperature, sieves and drum polletizing, making granularity is 0.5mm particle powderEnd, then by particle powder at 1850 DEG C of temperature, in vacuum tank, vacuum solid solution 3 hours, is finally organized as（W_0.17Ti_0.26Nb_0.36Zr_0.21) the WTNZ3 solid-solution powder of C.

The performance indications of powder:

1) prepared powder is face-centered cubic crystal formation product, and several compounds have reached good solid solution, and Fig. 3 has shownThe XRD collection of illustrative plates of prepared solid-solution powder WTNZ3;

2) particle mean size of prepared powder is 1.5-2.0 μ m;

3) WTNZ3 solid solution chemical composition table 3

Table 3WTNZ3 chemical composition

Element	W%	Ti%	Nb%	Zr%	CT%	CF%	O%	N%
									Test value	29.47	11.27	30.6	17.58	10.63	0.16	0.15	0.15

Obtained powder composition conforms to design load substantially as can be seen from the above table, and oxygen content is very low≤and 0.20%, powder toolThere is higher purity (> 99%).

Embodiment 4

The solid solution WTNZ1 that the present invention is made substitutes tradition and makees train wheel machining cutter containing Ta solid solution TRC-50Tool, concrete test situation is as follows:

1) solid solution composition contrast

WTNZ1：（W_0.33Nb_0.33Zr_0.20Ti_0.13) C unit price: 980 yuan/kilogram

TRC-50：（W_0.30Ti_0.2Ta_0.5) C unit price: 2000 yuan/kilogram

2) identical addition hart metal product performance comparison

Two kinds of Hardmetal materials are prepared to two kinds of sintered carbide tool materials, chemistry under identical process conditionsComposition is respectively:

①WC-13%WTNZ1-6%Co②WC-13%TRC-50-6%Co

Its physical and mechanical property is as following table 4

Table 4 adds different solid solution cutter material performances

Numbering	Solid solution	Bending resistance Strong degree	Hardness HRa	Density	Metallographic structure
						①	WTNZ1	2160MPa	92	12.92	A00B00C00
②	TRC-50	1892MPa	92	14.03	A00B02C00

3) two kinds of cutter materials are made respectively to the cutter RCMX320900 and the RCMX250700 that become processing train wheel,And then go on-the-spot cutting checking to factory after identical coating process is processed, its result is as following table 5.

Table 5 Tool in Cutting result of the test

Numbering	Solid solution	The RCMX250700 life-span	The RCMX320900 life-span
				①	WTNZ1	8/sword	12/sword
②	TRC-50	7/sword	12/sword

As can be seen from the above table, the cutting ability of cutter is suitable, uses without Ta solid solution WTNZ1 and can substitute containing Ta completelySolid solution TRC-50 is applied in the matrix material of cutter of train wheel, in price, obviously reduces, and the cost performance of cutter moreHigh.

Claims (8)

1. a tungsten carbide niobium zirconium solid solution powder, is characterized in that, the chemical formula of described tungsten carbide niobium zirconium solid solution is（W_0.17-0.21Ti_0.24-0.29Nb_0.31-0.36Zr_0.19-0.22）C。

2. tungsten carbide niobium zirconium solid solution powder as claimed in claim 1, is characterized in that, the solid solution of described tungsten carbide niobium zirconiumThe chemical formula of body is (W_0.20Ti_0.24Nb_0.35Zr_0.21）C。

3. tungsten carbide niobium zirconium solid solution powder as claimed in claim 1, is characterized in that, the solid solution of described tungsten carbide niobium zirconiumThe chemical formula of body is (W_0.20Ti_0.28Nb_0.32Zr_0.20）C。

4. tungsten carbide niobium zirconium solid solution powder as claimed in claim 1, is characterized in that, the solid solution of described tungsten carbide niobium zirconiumThe chemical formula of body is (W_0.17Ti_0.26Nb_0.36Zr_0.21）C。

5. a method of preparing tungsten carbide niobium zirconium solid solution powder as described in one of claim 1-4, comprises the following steps:

1) take respectively by weight 30～35 parts of WC, 30～35 parts of NbC, 17～22 parts of ZrC, 15～20 parts of TiO₂And 7～9Part hydrocarbon black powder, is mixed to get raw mixture;

2), using alcohol as ball-milling medium, obtain raw mixture slip by rolling ball milling;

3) described raw mixture slip is dry, then wipe sieve, drum polletizing, obtain compound;

4) described compound is reacted to 2～4h under 1700～1900 DEG C of conditions, obtain tungsten carbide niobium zirconium solid solution powder.

6. method as claimed in claim 5, is characterized in that step 2) in add the poly-second of raw mixture quality 2～5%Glycol.

7. method as claimed in claim 5, is characterized in that, in step 3), dry condition is-0.02～-0.08MPa、70～80℃。

8. method as claimed in claim 5, is characterized in that, described compound granularity is 0.5～1mm.