CN101418394A - Superhard composite material and method for preparation thereof - Google Patents
Superhard composite material and method for preparation thereof Download PDFInfo
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- CN101418394A CN101418394A CNA2007101668871A CN200710166887A CN101418394A CN 101418394 A CN101418394 A CN 101418394A CN A2007101668871 A CNA2007101668871 A CN A2007101668871A CN 200710166887 A CN200710166887 A CN 200710166887A CN 101418394 A CN101418394 A CN 101418394A
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Abstract
The invention relates to a super-hard composite material. The preparation method for the composite material comprises the step of mixing ceramic phase powder and multi-element high-entropy alloy powder to form a mixture, a pressed mixture and a sintered mixture, so as to prepare the super-hard composite material. The multi-element high-entropy alloy is an alloy containing 5 to 11 main elements, and each main element accounts for 5 to 35 molar percent of the multi-element high-entropy alloy.
Description
[technical field]
The present invention relates to super-hard compound material, relate more specifically to the composition of the bond of this material application.
[background technology]
Super-hard compound material has had characteristics such as high rigidity, high thermal resistance, wear resistant since the initial stage nineteen twenty development because of it, promptly be regarded as quite successful matrix material and widely industry member adopt.Super-hard compound material for the most large, can roughly be divided into two big classes with the carbide super-hard compound material: (1) wolfram varbide (WC) is main super-hard compound material, and (2) titanium carbide (TiC) is main super-hard compound material.General super-hard compound material by two kinds diverse form constitute: a kind ofly formed as carbide such as wolfram varbide, titanium carbide, vanadium carbide, niobium carbide, chromium carbide, tantalum carbide and carbonitride, boride, oxide compound by all very high but ceramic phase particles such as carbide embrittlement easily of fusing point and hardness; Another kind of then be the low high bond (binder metals) of toughness of hardness.The bond that the wolfram varbide super-hard compound material uses is mostly based on cobalt (Co).The titanium carbide superhard alloy then usually with nickel or nickel-molybdenum alloy as bond.The technology system employing powder metallurgic method that this matrix material is made, promptly under sintering temperature, bond forms liquid phase or forms the eutectic liquid phase with carbide, utilizes capillarity that carbide particle is coated and interior poly-the contraction, obtains high sintered density.For more improving sintered density, also can adopt pressure sintering method (press sintering), or hot again isostatic pressing (hot isostatic pressing) behind the sintering, so super-hard compound material can manifest its high rigidity and wear resistant by carbide, bond then provides required toughness.
The super-hard compound material of above-mentioned two big classes often is applied on cutting tool, mould, instrument and the abrasion performance assembly, comprises lathe tool, milling cutter, reamer, planing tool, saw blade, drill bit, drift, shearing die, shaping mould, takes out molding, extrusion die, watch part, ballpoint pen pearl etc.Being most widely used wherein with the wolfram varbide super-hard compound material, according to different application requiring, the range of choice of super-hard compound material also thereby quite extensive, usually bond content is lower, the content of strengthening material is higher, and hardness and wear resistance all can increase, but opposite, toughness and shock-resistance also and then reduce, and more easily break.Therefore for requiring hard and attrition resistant application, the content of strengthening material must improve, and for the higher application of toughness reguirements, the content of strengthening material must reduce.In addition, for the assembly of using under wear-resistant components under the corrosive environment or the high temperature, characteristics such as its solidity to corrosion or scale resistance also all need to consider in the lump.Progress along with the epoch, the human living standard improves day by day, no matter be traditional industry or high-tech industry, demand and production for various spare parts grow with each passing day, and how to enhance productivity, prolongs life and reduce cost and become cutter, mould, instrument and wear member inevitable development trend.Yet the toughness of carbide super-hard compound materials such as traditional wolfram varbide, titanium carbide, temperature tolerance, wear resistance, solidity to corrosion, anti-stickiness are still normal under different application scenarios dislikes not enough.
The bond that traditional wolfram varbide super-hard compound material uses is based on cobalt, and minority is the alloy of iron, nickel or iron-cobalt-nickel.The drift material that Japanese Patent JP 8,319,532 proposes the tool erosion resistance is based on wolfram varbide, and the bond of use is a nickel-base material, and percentage composition is 5～15wt%, and wherein Ni-based bond also comprises extra 3～13wt% Cr except nickel
3C
2At Japanese Patent JP10, in 110,235, the bond of wolfram varbide super-hard compound material also contains vanadium, chromium, chromium carbide and vanadium carbide based on iron.In U.S. Pat 6,030, in 912, as WC+W
2The bond composition of C is: one or more metals in iron, cobalt, the nickel, content is carbide, nitride and the carbonitride of transition metals such as IVA, VA in 0.02～0.1wt% and one or more periodictables and VIA, and content is 0.3～3wt%.In U.S. Pat 6,241, in 799, with cobalt and/or nickel sintering metal as wolfram varbide, in order to suppress tungsten carbide crystal grain produces crystal grain-growth in sintering process phenomenon, the prescription of bond is: cobalt contain at most 90wt%, nickel contain at most 90wt%, chromium content between 3～15wt%, the high-content of tungsten and molybdenum is respectively 30wt% and 15wt%.
At present the area that has the call of wolfram varbide super-hard compound material is the China's Mainland, so the China's Mainland has considerable patent to be suggested, and most demand all is high strength, high rigidity, high tenacity and high abrasion resistance.As Chinese patent CN 1,548,567 with the bond of high mangaenese steel as wolfram varbide, and the composition of high mangaenese steel is the manganese of 14～18wt%, the nickel of 3～6wt%, the carbon of 0.9～1.9wt% and the iron of 74.1～82.1wt%, and this tungsten carbide material has high strength, high rigidity and high abrasion resistance.Also having many is the patents that add carbide in bond, as Chinese patent CN 1,554, the 789th, with 4～6wt% cobalt and 0.3～0.6wt% tantalum carbide as bond, and with this bond and tungsten carbide powder mixed sintering, can be than the tungsten carbide composite of high-wearing feature and high tenacity.Chinese patent CN 1,718,813rd for another example, with the chromium carbide of vanadium carbide+0.3～0.7wt% of cobalt+0.1～0.5wt% of 7～9wt% as bond, and with the wolfram varbide sintering, can get the tungsten carbide composite of higher-strength, high rigidity, high tenacity.
By the above-mentioned patent of enumerating and take a broad view of in the past prior art, always employed as can be known bond, still do not take off with single metallic element as principal element (〉 50wt%) or two metallic elements as the alloy formula of principal element (promptly the content summation of this two element accounts for most ratio), ceramic phases such as a spot of metallic element or carbide wherein mix.For improving this bond, the present invention uses polynary high-entropy alloy or high-irregularity alloy (high-entropy alloys) as bond, this alloy is promptly disclosed as No. the 193729th, TaiWan, China patent of invention, its alloy component range is for containing 5 to 11 kinds of major metal elements, and the total mole number of the mole number of each major metal element and this alloy than system between 5% to 30%; And the idea of this high-entropy alloy and effect also propose in the following research paper of delivering in 2004 by contriver's leaf of this patent is all luxuriant first: AdvancedEngineering Materials, the 6th volume, the 5th phase, the the 299th to 303 page, high-entropy alloy is defined as contains principal element more than 5 kinds, and the total mole number of the mole number of each principal element and this alloy than system between 5% to 35%.This invention system makes its bond can obtain the microstructure of heatproof and hardness and the heat-resistant, wear-resistant that hardness improves the bulk ceramics phase composite materials by the distinctive high entropy effect of high-entropy alloy, slow diffusional effect, lattice twisted effect and cocktail complex effect.In addition, utilize its slow diffusional effect, can make the bond of this invention when being sintered to liquid phase, atom is difficult for the transmission diffusion, can suppress ceramic phase crystal grain-growths such as wolfram varbide, titanium carbide, and then avoids sintered compact hardness, toughness, heatproof and wear resistance to descend.In addition, utilize the part element in the bond to combine, more can produce carbide extraly, utilize the interpolation of nickel, chromium element can improve solidity to corrosion again to increase hardness with carbon, utilize the interpolation of chromium, aluminium, element silicon can improve oxidation-resistance again, utilize the interpolation of copper can improve oilness again.Therefore by suitable alloy designs and proportioning, can bring into play different performances and increase work-ing life.Comparatively speaking, traditional bond principal element is less, and relatively poor aspect the variability of composition design, performance is also comparatively limited to.
[summary of the invention]
The invention provides a kind of production method of super-hard compound material, comprise and mix at least a ceramic phase powder and polynary high-entropy alloy powder, form mixture; Press the embryo mixture; And sintering mix, to form super-hard compound material; Wherein polynary high-entropy alloy is the alloy of 5 to 11 kinds of principal elements, and every kind of principal element accounts for 5 to 35 moles of % of polynary high-entropy alloy.
The invention provides a kind of super-hard compound material, comprise (a) at least a ceramic phase powder; And (b) polynary high-entropy alloy; Wherein polynary high-entropy alloy is the alloy of 5 to 11 kinds of principal elements, and every kind of principal element accounts for 5 to 35 moles of % of this polynary high-entropy alloy.
[description of drawings]
Fig. 1 is the experiment flow of the embodiment of the invention;
Fig. 2 is the X light diffracting analysis figure of the polynary high-entropy alloy A1-A8 powder of the embodiment of the invention;
Fig. 3 is the X light diffracting analysis figure of the polynary high-entropy alloy B2 powder of the embodiment of the invention through the different ball milling time;
Fig. 4 is the X light diffracting analysis figure of the polynary high-entropy alloy B1-B3 and the mixed powder after the WC powder mixing and ball milling of the embodiment of the invention;
Fig. 5 is that the hardness of each sintering test piece of the embodiment of the invention is to different measuring variation of temperature curve;
Fig. 6 is the X light diffracting analysis figure of the high-entropy alloy C1 powder of the embodiment of the invention;
Fig. 7 is the X light diffracting analysis figure of the high-entropy alloy D1 powder of the embodiment of the invention;
Fig. 8 is the X light diffracting analysis figure of the high-entropy alloy E1 powder of the embodiment of the invention; And
Fig. 9 is the X light diffracting analysis figure of the high-entropy alloy F1 powder of the embodiment of the invention.
[embodiment]
The present invention proposes the bond of polynary high-entropy alloy as ceramic phases such as wolfram varbide, titanium carbides, improves the performance of super-hard compound material, to improve the work-ing life of different application.One of the present inventor Ye Junwei once developed high-irregularity multi-element alloy (claiming polynary high-entropy alloy again), disclosed as No. the 193729th, TaiWan, China patent of invention, its alloy component range is for containing 5 to 11 kinds of major metal elements, and the total mole number of the mole number of each major metal element and this alloy is than between 5% to 30%.In addition, this patent inventor's leaf is all luxuriant also to be proposed research paper with the idea of high-entropy alloy and effect first in 2004 and is published in: Advanced Engineering Materials, the 6th volume, the 5th phase, the the 299th to 303 page, in this paper, high-entropy alloy is defined as and contains principal element more than 5 kinds, and the total mole number of the mole number of each principal element and this alloy is than between 5% to 35%.The forming method of this high-entropy alloy can be fusion casting, forging method or powder metallurgic method.Because this alloy has high entropy effect, slow diffusional effect, lattice twisted effect, reaches the cocktail complex effect, its microstructure and intensity have good temperature tolerance, as bond the time, can improve the temperature tolerance of this matrix material.In addition, its slow diffusional effect can make bond of the present invention when being sintered to liquid phase, and atom is difficult for the transmission diffusion, can suppress ceramic phase crystal grain-growths such as wolfram varbide, titanium carbide, and then avoids hardness, toughness, heatproof and wear resistance to descend.In addition, utilize the part element in the bond to combine, more can additionally produce carbide to increase hardness with carbon.Add nickel, the chromium element can improve solidity to corrosion, can improve oxidation-resistance and add chromium, aluminium, element silicon.Comprehensive, high-entropy alloy can provide different improved properties and application.
In order to improve ceramic phase grain refining and the uniformly dispersing that coking property makes carbide, the present invention makes the even and refinement of the preceding powder mixes of sintering with machine-alloying (mechanical alloying).So-called machine-alloying is to utilize high-energy ball milling or bump processing procedure, makes that powder mixes repeatedly, cold welding, the deformational behavior with particulate cold welding again of breaking, and reaches the mixing purpose of alloying and compoundization at last.So mixed powder of the present invention, comprise mixing of element state powder and ceramic phase powder such as metallic carbide, or the mixing of powdered alloy and ceramic phase powder such as carbide, or the mixing of element state powder and ceramic phase powder such as alloy attitude powder and carbide, can obtain down columns item feature through machine-alloying: (1) can make the element state powder form alloying; (2) can make the further refinements of ceramic phase particles such as carbide; (3) can form the alloy powder that composition is even and particle is tiny, and bond evenly is coated on the outside surface of ceramic phase particles such as every kind of carbide.Ceramic phase powder such as carbide can be wolfram varbide or titanium carbide, and the weight ratio of ceramic phase powder and polynary high-entropy alloy is between between the 5:95 to 40:60.
Aspect sintering process, ceramic phase of the present invention/polynary high-entropy alloy super-hard compound material is similar to super-hard compound materials such as traditional tungsten carbide/cobalts, must be earlier through degreasing, degasification again through sintering or liquid phase sintering, the last cold taking-up of stove, wherein also presintering in the stove of lower temperature in advance, take out after suitable shape is processed in operations such as cutting, melt down last sintering again.In order further to improve sintered density, also can adopt pressure sintering method (press sintering), or hot again isostatic pressing (hot isostatic pressing) behind the sintering.Again, degreasing wherein, degasification and sintering atmosphere can adopt vacuum method also can adopt argon gas or its gas mixture protection method to carry out.Because of the difference of bond, sintering temperature is slightly variant.In embodiments of the present invention, can obtain good liquid phase sintering at 1300 to 1500 ℃.In embodiments of the present invention, the super-hard compound material that forms behind the sintering contains above-mentioned at least a ceramic phase powder and above-mentioned polynary high-entropy alloy, wherein this polynary high-entropy alloy is the alloy of 5 to 11 kinds of principal elements, and every kind of principal element accounts for 5 to 35 moles of % of this polynary high-entropy alloy.The weight ratio of above-mentioned ceramic phase powder and polynary high-entropy alloy can be between between the 5:95 to 40:60.In embodiments of the present invention, the hardness of super-hard compound material is between between the HV800 to 2400.
For making the clearer feature of the present invention of those skilled in the art, the spy is schematically illustrated in following embodiment.
Embodiment 1
The experiment flow of present embodiment utilizes the mechanical ball milling mode to form polynary high-entropy alloy powder multiple pure metal or alloy powder earlier as shown in Figure 1.Again polynary high-entropy alloy is mixed and ball-milling processing according to different ratios with tungsten carbide powder, make it to become mixed uniformly composite material powder.Then more uniform wolfram varbide-polynary high-entropy alloy mixed powder is made the super-hard compound material sintered compact through overvoltage embryo and high temperature sintering, at last sintered compact is done test and analyzed.Present embodiment system adopts aluminium, chromium, copper, iron, manganese, titanium and seven kinds of pure metal powders of vanadium to make polynary high-entropy alloy powder.Utilize field mouth laboratory method L
82
7Orthogonal table preparation A series alloy, listed as table one.
Table one
Annotate: in the table in the A1 alloy in the constituent content the deputy difference of radix point be in order to make the element total content be necessary for 100%.
Powder after the configuration obtained polynary high-entropy alloy powder through 18 hours behind the ball milling, the X-ray diffractogram of each powder and analysis have presented the alloying phenomenon of certain degree as shown in Figure 2.Then again with tungsten carbide powder according to the proportional arrangement of table two, mechanical ball milling and press the embryo sintering, the hardness of sintering gained wolfram varbide/polynary high-entropy alloy sintered compact is as shown in Table 2.In table two, by adjusting the matrix material that high-entropy alloy and the ratio of wolfram varbide can obtain the different hardness scope, so that the application of different requirements to be provided.
Table two
| Test piece number | The alloy powder weight ratio | WC powder weight ratio | Hardness (Hv) |
| A1W-20 | 20％A1 | 80％ | 1312 |
| A2W-20 | 20％ |
80％ | 1405 |
| A3W-20 | 20％A3 | 80％ | 1352 |
| A4W-20 | 20％A4 | 80％ | 1607 |
| A5W-20 | 20％A5 | 80％ | 1423 |
| A6W-20 | 20％A6 | 80％ | 1501 |
| A7W-20 | 20％A7 | 80％ | 1532 |
| A8W-20 | 20％A8 | 80％ | 1468 |
Embodiment 2
The present embodiment experiment flow becomes polynary high-entropy alloy powder with aluminium, chromium, cobalt, copper, iron, six kinds of metallic element powders of nickel mixing and ball milling also as shown in Figure 1, and allocation ratio is the B series alloy shown in the table three.Be example with the B2 powder wherein, the relation of different ball milling times and polynary high-entropy alloy crystal structure shows that the ball milling more than 24 hours can get alloying completely shown in the X light diffracting analysis of Fig. 3, form single FCC phase sosoloid.
Table three
Table four illustrates for the code name of its powder configuration, three kinds of alloys in this table through with WC powder mixing and ball milling after the X light diffracting analysis done of mixed powder as shown in Figure 4, can find out only to present WC and single FCC mixed phase structure mutually.Remaining powder configuration also presents same mixed phase structure.
Table four
| Test piece number | The alloy powder weight ratio | WC powder weight ratio |
| B1W-20 | 20％ |
80％ |
| B2W-20 | 20％ |
80％ |
| B3W-20 | 20％B3 | 80％ |
Mixed powder press behind the embryo sintering condition as shown in Table 5:
Table five
| Between heating zone (℃) | Temperature rise rate (℃/min) | Hold the temperature time (min) | Sintering atmosphere Ar+10wt%H 2 |
| Room temperature～300 | 3 | 30 | |
| 300～500 | 3 | 60 | Ar+10wt％H 2 |
| 500～1250 | 6 | 30 | Vacuum |
| 1250～1385 | 3 | 60 | Vacuum |
| 1385～room temperature | Stove is cold | Vacuum |
Table six illustrates density, normal temperature hardness and the wear resistant that the B2 powder of different ratios and WC powder are pressed test piece behind embryo and the sintering, as expected, reduces with the strong phase content of WC, and normal temperature hardness and wear resistance can have a declining tendency.Fig. 5 shows WC content more after a little while, the typical phenomenon that hardness curve down descends equally for the hardness of each sintering test piece hardness test gained under differing temps varies with temperature curve.Other B series alloy also presents similar characteristic to the sintered compact of WC powder different ratios, and the scope of its variation is all arranged.Therefore the composite hardness by this series alloy gained presents different scopes, also shows and can be controlled hardness by the adjustment of proportioning, so that the different application that require to be provided.In addition, this high-entropy alloy presents outstanding solidity to corrosion because contain high-load chromium and nickel, can form fine and close pellumina because contain aluminium again, present outstanding high temperature oxidation resistance, so its super-hard compound material can be used for having corrosive occasion and pyritous occasion.
Table six
| Test piece number | B2 alloy powder ratio (wt%) | WC powder ratio (wt%) | Density (g/cm 3) | Hardness (Hv) | Wear resistant (m/mm 3) |
| B2W-10 | 10 | 90 | 12.71 | 1512 | 38 |
| B2W-15 | 15 | 85 | 12.28 | 1455 | 24 |
| B2W-20 | 20 | 80 | 11.92 | 1413 | 10 |
| B2W-25 | 25 | 75 | 11.55 | 1389 | 7 |
| B2W-30 | 30 | 70 | 11.27 | 1225 | 5 |
| B2W-35 | 35 | 65 | 10.79 | 1023 | 4 |
The present embodiment experiment flow carries out ball milling with carbon, chromium, nickel, titanium, v element powder and forms polynary high-entropy alloy also as shown in Figure 1, and its allocation ratio is the C1 alloy shown in the table seven; Fig. 6 is the X light diffracting analysis of high-entropy alloy C1 powder, and the complete alloying of powder behind the demonstration ball milling also forms single BCC solid solution phase.
Table seven
Table eight is the C1 alloy powder and sintered density and the normal temperature hardness of WC powder under different sintering temperatures of different ratios.For example the hardness of wolfram varbide-20% C1 alloy sintered compact can reach Hv 1825.And the normal temperature hardness of wolfram varbide-15% C1 alloy sintered compact is more up to Hv 1972.The difference of this durometer level also shows and can be controlled by the adjustment of proportioning, so that the different application that require to be provided.
Table eight
| Test piece number | C1 alloy powder ratio (%) | WC powder ratio (%) | Sintering temperature (℃) | Density (g/cm 3) | Hardness (Hv) |
| C1W-151 | 15 | 85 | 1375 | 12.00 | 1633 |
| C1W-152 | 15 | 85 | 1425 | 11.56 | 1972 |
| C1W-153 | 15 | 85 | 1450 | 12.13 | 1732 |
| C1W-201 | 20 | 80 | 1280 | 12.19 | 1366 |
| C1W-202 | 20 | 80 | 1320 | 12.45 | 1825 |
| C1W-203 | 20 | 80 | 1385 | 12.18 | 1302 |
Embodiment 4
The present embodiment experiment flow carries out ball milling with carbon, chromium, iron, titanium, v element powder and forms polynary high-entropy alloy also as shown in Figure 1, and its allocation ratio is the D1 alloy shown in the table nine.Fig. 7 is the X light diffracting analysis of high-entropy alloy D1 powder, and the complete alloying of powder behind the demonstration ball milling also forms single BCC solid solution phase.
Table nine
Table ten is the D1 alloy powder and sintered density and the normal temperature hardness of WC powder under different sintering temperatures of different ratios.The difference of this durometer level also shows and can be controlled by the adjustment of proportioning, so that the different application that require to be provided.
Table ten
| Test piece number | D1 alloy powder ratio (%) | WC powder ratio (%) | Sintering temperature (℃) | Density (g/cm 3) | Hardness (Hv) |
| D1W-151 | 15 | 85 | 1375 | 11.64 | 2224 |
| D1W-152 | 15 | 85 | 1425 | 11.65 | 2278 |
| D1W-153 | 15 | 85 | 1450 | 11.58 | 2278 |
| D1W-201 | 20 | 80 | 1385 | 11.93 | 1971 |
| D1W-202 | 20 | 80 | 1450 | 11.76 | 2033 |
Embodiment 5
The present embodiment experiment flow carries out ball milling with carbon, chromium, cobalt, titanium, v element powder and forms polynary high-entropy alloy also as shown in Figure 1, and its allocation ratio is the E1 alloy shown in the table ten one; Fig. 8 is the X light diffracting analysis of high-entropy alloy E1 powder, and the complete alloying of powder behind the demonstration ball milling also forms single BCC solid solution phase.
Table ten one
Table ten two is the 15wt%E1 alloy powder and sintered density and the normal temperature hardness under different sintering temperatures after the composite granule of 85wt%WC powder is pressed embryo.The difference of this durometer level also shows and can be controlled by the adjustment of proportioning, so that the different application that require to be provided.
Table ten two
| Test piece number | D1 alloy powder ratio (%) | WC powder ratio (%) | Sintering temperature (℃) | Density (g/cm 3) | Hardness (Hv) |
| E1W-151 | 15 | 85 | 1425 | 11.95 | 2213 |
| E1W-152 | 15 | 85 | 1450 | 12.38 | 2318 |
Embodiment 6
The present embodiment experiment flow carries out ball milling with carbon, chromium, iron, nickel, titanium, v element powder and forms polynary high-entropy alloy also as shown in Figure 1, and its allocation ratio is the F1 alloy shown in the table ten three; Fig. 9 is the X light diffracting analysis of high-entropy alloy F1 powder, and the complete alloying of powder behind the demonstration ball milling also forms single BCC solid solution phase.
Table ten three
Table ten four is a 15wt% F1 alloy powder and sintered density and the normal temperature hardness under different sintering temperatures after the composite granule of 85wt% WC powder is pressed embryo.The difference of this durometer level also shows and can be controlled by the adjustment of proportioning, so that the different application that require to be provided.
Table ten four
| Test piece number | D1 alloy powder ratio (%) | WC powder ratio (%) | Sintering temperature (℃) | Density (g/cm 3) | Hardness (Hv) |
| F1W-151 | 15 | 85 | 1375 | 11.85 | 1907 |
| F1W-152 | 15 | 85 | 1425 | 12.15 | 2050 |
| F1W-153 | 15 | 85 | 1450 | 11.95 | 1791 |
Embodiment 7
The present embodiment experiment flow also as shown in Figure 1, employed bond is as the B2 high-entropy alloy powder of embodiment 2, employed strengthening material then changes the titanium carbide powder into, and table ten five is that the composite material powder under the different proportionings is pressed behind the embryo sintered compact normal temperature hardness under 1385 ℃ of sintering temperatures.The difference of this durometer level also shows and can be controlled by the adjustment of proportioning, so that the different application that require to be provided.
Table ten five
| Test piece number | The alloy powder weight ratio | TiC powder weight ratio | Hardness (Hv) |
| B2T-10 | 10％B2 | 90％ | 1176 |
| B2T-15 | 15％B2 | 85％ | 1705 |
| B2T-20 | 20 |
80％ | 1937 |
| B2T-25 | 25％B2 | 75％ | 1774 |
| B2T-40 | 40 |
60％ | 1678 |
| B2T-60 | 60 |
40％ | 1266 |
Embodiment 8
The present embodiment experiment flow carries out ball milling with cobalt, chromium, iron, nickel, titanium elements powder and forms polynary high-entropy alloy also as shown in Figure 1, and its allocation ratio is the G1 alloy shown in the table ten six.
Table ten six
Table ten seven is that the alloy powder G1 of different ratios and titanium carbide powder are pressed behind the embryo in sintering temperature 1380.Sintered compact normal temperature hardness under the C.The difference of this durometer level also shows and can be controlled by the adjustment of proportioning, so that the different application that require to be provided.In addition, this high-entropy alloy presents outstanding solidity to corrosion and high temperature oxidation resistance because contain high-load chromium and nickel, can be used for having corrosive occasion and pyritous occasion.
Table ten seven
| Test piece number | The alloy powder weight ratio | TiC powder weight ratio | Hardness (Hv) |
| G1T-10 | 10％G1 | 90％ | 1884 |
| G1T-15 | 15％G1 | 85％ | 1754 |
| G1T-20 | 20 |
80％ | 1876 |
| G1T-30 | 30 |
70％ | 1525 |
| G1T-40 | 40 |
60％ | 1223 |
| G1T-60 | 60 |
40％ | 809 |
Do the measurement of destruction toughness at C1W and two kinds of sintered compacies of D1W, and compare with commercial wolfram varbide, table ten eight is the hardness of four kinds of materials and destroys toughness KIC.The hardness that can find out C1W and two kinds of sintered compacies of D1W all is higher than commercial wolfram varbide, in addition, destroys toughness and also is higher than commercial wolfram varbide.Hence one can see that, and the wolfram varbide/polynary high-entropy alloy super-hard compound material also wolfram varbide super-hard compound material of comparable conventional commercial has more the advantage of high rigidity and high tenacity.
Table ten nine
Comprehensively above-mentioned, the present invention system is bond with polynary high-entropy alloy and is strengthening material and makes super-hard compound material through machine-alloying and liquid phase sintering with ceramic phases such as carbide as can be known.Selection by suitable element, ceramic phase and processing procedure, can offer the novel super-hard matrix material of a kind of different hardness of industry, wear resistant, erosion resistance, scale resistance, toughness, normal temperature hardness and hot hardness, to promote the application that this super-hard compound material requires in difference.
Though the present invention discloses as above with a plurality of preferred embodiments; right its is not in order to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; Ying Kezuo changes arbitrarily and retouches, so protection scope of the present invention should be as the criterion with the claims restricted portion.
Claims (14)
1. the production method of a super-hard compound material comprises:
Mix at least a ceramic phase powder and polynary high-entropy alloy powder, form mixture;
Press this mixture of embryo; And
This mixture of sintering is to form super-hard compound material;
Wherein this polynary high-entropy alloy is the alloy of 5 to 11 kinds of principal elements, and every kind of principal element accounts for 5 to 35 moles of % of this polynary high-entropy alloy.
2. the production method of super-hard compound material as claimed in claim 1, the step that wherein forms this mixture comprises machine-alloying.
3. the production method of super-hard compound material as claimed in claim 1, wherein the step of this mixture of sintering lies in the vacuum cavity and carries out.
4. the production method of super-hard compound material as claimed in claim 1, wherein the step of this mixture of sintering lies under the mixed gas of argon gas and hydrogen and carries out.
5. the production method of super-hard compound material as claimed in claim 1, wherein this ceramic phase powder comprises metallic carbide.
6. the production method of super-hard compound material as claimed in claim 5, wherein these metallic carbide comprise wolfram varbide or titanium carbide.
7. the production method of super-hard compound material as claimed in claim 1, wherein first prime system of comprising of this polynary high-entropy alloy be selected from periodictable carbon, aluminium, chromium, cobalt, copper, iron, nickel, vanadium, manganese, and titanium elements group in multiple element.
8. the production method of super-hard compound material as claimed in claim 1, wherein the weight ratio of this ceramic phase powder and this polynary high-entropy alloy is between between the 5:95 to 40:60.
9. super-hard compound material comprises:
(a) at least a ceramic phase powder; And
(b) polynary high-entropy alloy;
Wherein this polynary high-entropy alloy is the alloy of 5 to 11 kinds of principal elements, and every kind of principal element accounts for 5 to 35 moles of % of this polynary high-entropy alloy.
10. super-hard compound material as claimed in claim 9, wherein this ceramic phase powder comprises metallic carbide.
11. super-hard compound material as claimed in claim 10, wherein these metallic carbide comprise wolfram varbide or titanium carbide.
12. super-hard compound material as claimed in claim 9, wherein first prime system of comprising of this polynary high-entropy alloy be selected from periodictable carbon, aluminium, chromium, cobalt, copper, iron, nickel, vanadium, manganese, and titanium elements group in multiple element.
13. super-hard compound material as claimed in claim 9, wherein the weight ratio of this ceramic phase powder and this polynary high-entropy alloy is between between the 5:95 to 40:60.
14. super-hard compound material as claimed in claim 9, wherein the hardness of this super-hard compound material is between between the HV800 to 2400.
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Open date: 20090429 |