CN109338193B - Coreless-ring structure metal ceramic alloy and preparation method thereof - Google Patents
Coreless-ring structure metal ceramic alloy and preparation method thereof Download PDFInfo
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- 229910002109 metal ceramic alloy Inorganic materials 0.000 title claims abstract description 19
- 239000000078 metal ceramic alloy Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 99
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011195 cermet Substances 0.000 claims abstract description 18
- 239000011858 nanopowder Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims description 55
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000000498 ball milling Methods 0.000 claims description 37
- 239000000956 alloy Substances 0.000 claims description 34
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 33
- 238000004321 preservation Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 31
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000005238 degreasing Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 239000012188 paraffin wax Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 239000002826 coolant Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 229910003178 Mo2C Inorganic materials 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000004663 powder metallurgy Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to the technical field of preparation of metal ceramic materials, and relates to a coreless-ring junctionA metal ceramic alloy and a preparation method thereof. The coreless-ring structure metal ceramic alloy comprises, by weight, 10-55% of Ti (C, N) micron powder, 10-55% of (Ti, M) (C, N) micron powder, 10-55% of Ti (C, N) submicron or/and nano powder, 10-55% of (Ti, M) (C, N) submicron or/and nano powder, 5-20% of WC, 0-30% of TiC, 0-30% of TiN, 0-20% of Co, 0-20% of Ni, 0-10% of Cr, and 0-15% of Mo2C，0～10％TaC/NbC，0～2.5％VC，0～5％Cr2C30-1.2% of carbon black is mixed according to a certain proportion to prepare a mixture, and the mixture is ball-milled, sieved and molded to prepare a blank, and the blank is sintered and cooled to prepare the cermet material with the coreless-ring structure. The invention adopts a powder metallurgy method to prepare the metal ceramic alloy without the core-ring structure, and overcomes the technical difficulty that the microstructure core-ring thickness is difficult to control in the traditional preparation process of the metal ceramic with the core-ring structure.
Description
Technical Field
The invention belongs to the technical field of preparation of metal ceramic materials, and particularly relates to a coreless-ring structure metal ceramic alloy and a preparation method thereof.
Background
The Ti (C, N) -based metal ceramic alloy has unique performance advantages, has the characteristics of excellent wear resistance, high-temperature and high hardness, thermal stability, oxidation resistance, adhesion resistance and the like at 700-1100 ℃, and is one of the main substrate materials for a high-temperature and high-speed cutting tool. The alloy also has stable high-temperature strength, good friction performance and acid-base corrosion resistance, and can be widely applied to various industries and fields of high-temperature components of engines, petrifaction, chemical fibers and the like. Compared with the traditional WC-Co hard alloy, the material fills the blank between the requirements of the hard alloy and the ceramic cutter and other materials, and effectively saves the valuable rare metals such as Co, Ta, W and the like which are necessary for the common hard alloy cutter. The development of high-performance (high hardness, high strength, high comprehensive wear resistance, referred to as "three-high") and long-life Ti (C, N) -based cermet alloy materials has become the focus of Ti (C, N) -based cermet research in recent years.
At present, the field mainly takes the preparation of Ti (C, N) -based cermet with a typical core-ring structure as a main method, and a core-ring shell layer formed by (Ti, M) (C, N) composite solid solution can be formed on a hard phase during sintering, but the ring shell layer is not complete usually, so that a part of Ti (C, N) in the hard phase and a bonding phase metal can be in direct contact, the hard phase is decarburized, and the like, and the fracture toughness and the bending strength of the cermet are reduced. Meanwhile, the thickness of the microcosmic core-ring structure has great influence on the hardness, the fracture toughness and the bending strength of the prepared alloy, and the excessive thickness or the excessive thinness of the microcosmic core-ring structure of the alloy formed in the preparation process are not favorable for the final comprehensive performance. Therefore, the difficulty of the control process of the thickness of the microscopic core-ring structure is great, so that the stability of the material performance is not easy to guarantee.
Disclosure of Invention
In view of the above problems, a first object of the present invention is to provide a coreless-ring structural cermet alloy to solve the problem that the annular shell is incomplete, so that a portion of Ti (C, N) in the hard phase and the binder phase metal may directly contact each other, thereby causing decarburization of the hard phase, and thus the fracture toughness and bending strength of the cermet may decrease; the second objective of the present invention is to provide a method for preparing a cermet alloy with a coreless-ring structure to solve the problem of difficulty in controlling the thickness of the coreless-ring structure.
The metal ceramic alloy comprises, by weight, 10-55% of Ti (C, N) micron powder, 10-55% of (Ti, M) (C, N) micron powder, 10-55% of Ti (C, N) submicron or/and nano powder, 10-55% of (Ti, M) (C, N) submicron or/and nano powder, 5-20% of WC (wolfram), 0-30% of TiC, 0-30% of TiN, 0-20% of Co, 0-20% of Ni, 0-10% of Cr and 0-15% of Mo2C，0～10％TaC/NbC，0～2％VC，0～5％Cr2C30 to 1.2% of carbon black. It should be noted here that TiN, Co, Ni, Cr, Mo may be selected as the components2C、TaC/NbC、VC、Cr2C3And any one, several or all of carbon black.
Wherein, M element in the (Ti, M) (C, N) micron powder and the (Ti, M) (C, N) submicron or/and nanometer powder is one or more of Mo, W, Ta, Nb, Zr, Cr, V and other solid solution powder; the Ti (C, N), (Ti, M) (C, N) micron powder and the C, N in the Ti (C, N), (Ti, M) (C, N) submicron or/and nanometer scale powder adopt one of C/N atomic ratio 7/3, 6/4 or 5/5, and the mass fraction is 5/5. Here, the submicron powder and/or the nanopowder are any one of submicron powder of (Ti, M) (C, N), nanopowder of (Ti, M) (C, N), or mixed powder of submicron powder of (Ti, M) (C, N) and nanopowder of (Ti, M) (C, N) that can be selected in a specific experimental process.
Specifically, the hard phase is mainly selected from Ti (C, N), (Ti, M) (C, N) powder, and additionally comprises one or more of WC, TiC, TiN and TaC powder, wherein M element in the (Ti, M) (C, N) powder is selected from Mo, W, Ta, Nb, Zr, Cr, V and the like. The binder phase is one or more of Co, Ni, Cr, Fe, etc. Mo is selected as additive phase2C. Any one of TaC and NbC; enhanced phase selectionWith VC, Mn2C，ZrC、Cr2C3And any or all of the carbon black powder as a preliminary raw material.
Preferably, the composition comprises, by weight, 15-45% of Ti (C, N), 15-45% (Ti, M) (C, N) micron powder, 6-15% of Ti (C, N) micron or/and nano powder, 7-15% (Ti, M) (C, N) submicron or/and nano powder, 12-18% of WC, 0.5-15% of TiC, 0.5-15% of TiN, 8-15% of Co, 3-8% of Ni, 1-5% of Cr, and 5-12% of Mo2C，2～10％TaC/NbC，0.3～1.0％VC，0.5～1.2％Cr2C30.0 to 1.0% of carbon black.
A preparation method of a coreless-ring structure metal ceramic alloy comprises the following steps:
(1) the preparation method comprises the following steps of weighing the raw materials listed above according to a certain proportion, mixing, adding a grinding medium, a dispersing agent and a forming agent, and uniformly mixing to obtain the prepared raw materials.
(2) And (3) putting the prepared raw materials into a grinding hard alloy ball milling tank of a ball mill, and performing ball milling to obtain a mixed material.
(3) And (3) sieving the mixed material by a sieve of 150-250 meshes or performing spray granulation.
(4) And directly filling the sieved mixed material into a mold to be pressed into a blank.
(5) Firstly, the compression molding blank is put into a high vacuum degreasing positive pressure sintering rapid cooling furnace, gas in the furnace body is pumped out to ensure that the furnace body is vacuum and the vacuum degree is not more than 15Pa, then a sintering furnace power supply is started, the heating degreasing stage, the solid phase sintering stage, the liquid phase sintering stage and the rapid cooling stage are sequentially carried out, and then the metal ceramic alloy is taken out of the furnace and taken out.
Further, the grinding medium in the step (1) is hexane or absolute ethyl alcohol, and the mass fraction of the grinding medium in the total amount of the grinding medium is 0.5-1.8%; the dispersing agent is dodecyl benzene sulfonic acid, stearic acid or ethofenamine, and the mass fraction of the dispersing agent is 0.1-0.5%; the forming agent is one or more of gasoline and rubber, paraffin, polyvinyl alcohol, synthetic rubber, ethylene glycol or SBS as solute, and the mass fraction is 2-5%.
Further, the ball mill in the step (2) is a rolling ball mill or a planetary ball mill, the ball diameter of the hard alloy ball is 6.25-10 mm, and the ball-to-material ratio is 8-15: l; the ball milling speed of the ball mill is 70-120 r/min, the ball milling time is 48-144 h, and the preferable time is 72-116 h.
Further, the pressure in the mold is 150-450 MPa, and the pressure maintaining time is 15-300 s, preferably 15-30 s.
Further, the heating and degreasing process is carried out according to the working procedures of preheating, gas introduction, temperature rise, heat preservation and temperature control, the heating vacuum degreasing temperature is raised to 450-800 ℃, the preferred temperature is 500 ℃, the heat preservation and temperature control time is 50-100 min, and the temperature deviation is controlled to be +/-0.50 ℃. Here, it should be noted that the gas to be introduced is any one group of pure nitrogen, nitrogen and hydrogen, nitrogen and argon, methane and argon.
Further, in the solid phase sintering stage, the heating temperature is increased from 450-800 ℃ to 1280-1350 ℃, the heating rate is not more than 5 ℃/min, the heat preservation and temperature control time is set to be 45-90 min respectively at the sintering temperature of 850-950 ℃, 1220-1280 ℃ and 1280-1350 ℃, and the temperature deviation is controlled to be +/-0.50 ℃. It should be noted that, the sintering temperature is kept at a specific temperature within the range of each stage, and then the specific temperature deviation is controlled within ± 0.50 ℃.
Further, when the solid phase sintering stage is finished and then the liquid phase sintering stage is carried out, the temperature is increased to 1430-1470 ℃ at the temperature rising rate of 2-5 ℃/min, the heat preservation time of the liquid phase sintering stage is 45-90 min, meanwhile, 1-10 MPa of argon gas is introduced, the purity of the argon gas is more than 99.995%, the air pressure is preferably 2-5 MPa, and the temperature deviation is controlled within +/-0.50 ℃.
Further, after the liquid phase sintering stage is finished, a rapid cooling stage is carried out, the temperature is slowly cooled to 1200 ℃, argon gas is filled as a cooling medium to carry out rapid cooling until the temperature reaches the room temperature, the purity of the argon gas is more than 99.995%, and the cooling rate is more than 35 ℃/min until the temperature reaches the room temperature.
Compared with the prior art, the invention has the following beneficial effects:
(1) the cermet alloy provided by the invention adopts multiple alloying elements to optimize a hard phase, a wetting phase and a strengthening phase of the cermet material, reduces the expansion coefficient of the cermet alloy by regulating and modifying the effective phases of the metal phase or the ceramic phase through the alloying elements, and couples and matches a matrix hard phase and a bonding phase;
(2) the solid solution diffusion reaction of each element of (Ti, M) (C, N) is promoted to form a transition phase through sintering at the solid phase and liquid phase sintering stages, so that the microcrystal interface bonding method without obvious core-ring transition between a Ti (C, N) black core phase and a Co (Ni, Cr, Mn, Fe) and other metal bonding phases is realized;
(3) submicron or nanometer powder particles are adopted to optimize and increase the fracture toughness of the alloy and improve the comprehensive properties of the alloy, such as hardness, bending strength and the like, the submicron or nanometer particles are completely or partially dissolved into a bonding phase to form a multi-element transition phase in a liquid phase sintering stage, and meanwhile, the existence of undissolved submicron and nanometer particles is beneficial to stress relief;
(4) the preparation method provided by the invention sets a pressure sintering process schedule at the liquid phase sintering stage, forms a low-pressure sintering complete densification technology for the metal ceramic alloy, effectively inhibits the denitrification phenomenon in the alloy sintering process and optimizes the C, O effect; in the cooling stage, a component supercooling technology is adopted, and a method for preparing the alloy by filling high-purity medium argon and rapidly cooling is adopted, so that a stable phase interface is formed between the hard phase and the bonding metal, the uniform transition of the components of the alloy elements is realized, and the homogeneity of the microstructure is formed.
In conclusion, the microstructure of the prepared metal ceramic alloy can be well controlled, the prepared metal ceramic alloy can provide a good initial structure state and an excellent comprehensive performance matrix for widely applied cutter materials and devices, the use of strategic alloy elements such as W, Co, Ta and the like is greatly saved, and the production cost of the alloy is effectively reduced.
Description of the drawings:
the present invention will be described in further detail with reference to the accompanying drawings and examples.
FIG. 1 is a microstructure view of a cermet alloy according to example 2 of the present invention under a scanning electron microscope of 5000 times;
FIG. 2 is a scanning electron microscope 20000 times lower line scanning element distribution diagram of the cermet alloy of example 2 of the present invention;
FIG. 3 is a microstructure of cermet alloy of example 2 according to the present invention under a scanning electron microscope of 20000 times;
FIG. 4 is an EDS energy spectrum of the black core hard phase detected in the position of the A point in FIG. 3 in example 2 of the invention;
FIG. 5 is an EDS energy spectrum of the homogeneous transition solid solution phase of the alloy composition detected at the position of the B point in FIG. 3 in example 2 of the present invention;
FIG. 6 is an EDS spectrum of the metal binding phase detected at the position of C point in FIG. 3 in example 2 of the present invention;
FIG. 7 is a phase distribution diagram of XRD ray diffraction of a cermet alloy of example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it is to be understood that various changes or modifications may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present application.
Wherein the solid solution powder of (Ti, M) (C, N) contains the components (for example, (Ti, W8, Mo5) (C)0.5,N0.5) Represents that W accounts for 8% of the total content, represents that Mo accounts for 5% of the total content, and the C/N atomic ratio is 0.5/0.5. The above powder components were weighed using a differential electronic balance.
Example 1
Ti(C0.5,N0.5) Micron powder size FSSS1.8 weighing 400g, (Ti, W8, Mo5, Ta2.5, Zr0.35) (C0.5,N0.5) Micron powder size FSSS1.5 weighing 1000g, Ti (C)0.5,N0.5) Submicron powder particle size FSSS0.8 weight 960g, (Ti, W8, Mo5) (C0.5,N0.5) The nanopowder with particle size FSSS0.1 weighed 840g, the WC powder with particle size FSSS0.8 weighed 800 g. 3500ml of ball milling medium absolute ethyl alcohol is weighed, 90g of forming agent is weighed by adopting polyvinyl alcohol, and 6g of dispersing agent is weighed by adopting ethoprol.
(1) Ball milling and mixing: putting the raw material powder prepared in the step (1) into YG6X alloy balls with the diameter of 10mm and absolute ethyl alcohol as ball milling media, adding 6g of dispersing agent ethoprol and 90g of forming agent polyvinyl alcohol into a clean stainless steel ball milling tank, and then ball milling for 144h on a roller ball mill with the ball-material ratio of 8:1 and the ball milling rotation speed of 70 r/min. Taking out the wet ground material, drying in a vacuum drying oven at 80 ℃ for 4h, homogenizing and crushing, and sieving the powder by adopting a sieve with 150 meshes to prepare granules with certain components and particle size requirements.
(2) And (2) directly filling the mixture powder sieved in the step (1) into a die, pressing for 15s under the pressure of 450MPa, and preparing the uniformly mixed powder into a blank.
(3) And (3) putting the blank body pressed in the step (2) into a sintering furnace according to the working procedures of preheating, heating up, heat preservation and temperature control, heating up to the temperature of 450 ℃ in vacuum degreasing, keeping the temperature for 50min, and controlling the temperature deviation to be +/-0.50 ℃.
(4) Solid-phase sintering stage: the heating temperature is increased from 450 ℃ to 1300 ℃, the heating rate is not more than 5 ℃/min, the heat preservation and temperature control time is 90min at the sintering temperature of 880 ℃, the heat preservation and temperature control time is 90min at the temperature of 1230 ℃, the heat preservation and temperature control time is 90min at the temperature of 1310 ℃, and the temperature deviation is controlled to be +/-0.50 ℃;
liquid phase sintering stage: the heating temperature is increased from 1330 ℃ to 1470 ℃, the heating rate is set to be within 5 ℃/min, simultaneously 1MPa of high-purity 99.9995 percent argon gas is introduced, the heat preservation and temperature control time period is set to be 45min when the sintering temperature is 1470 ℃, and the temperature deviation is controlled to be +/-0.50 ℃.
And (3) a cooling stage: slowly cooling to 1200 +/-0.5 ℃, rapidly cooling to room temperature, taking high-purity 99.9995% argon as a cooling medium, reaching the room temperature at a cooling rate of 37 ℃/min, discharging and taking out the metal ceramic alloy.
Example 2
Ti(C0.5,N0.5) Micron powder size FSSS1.5 weigh 830g, (Ti, W8, Mo5, Ta2.5, Zr0.35) (C0.5,N0.5) Micron powder size FSSS1.5 weigh 360g, Ti (C)0.5,N0.5) Submicron powder particle size FSSS0.8 weigh 820g, (Ti,W8,Mo5)(C0.5,N0.5) 390g for nanopowder particle size FSSS0.15, 320g for Ni powder with powder particle size FSSS1.5, 320g for Co powder with powder particle size FSSS1.2, 600g for WC powder with powder particle size FSSS0.8, and 600g for Mo powder with powder particle size FSSS1.52Weighing 360g of powder C; 3500ml of ball milling medium hexane is weighed, 160g of forming agent is weighed by adopting paraffin, and 8g of dispersing agent is weighed by adopting stearic acid.
(1) Ball milling and mixing: putting the raw material powder prepared in the step (1) into YG6X alloy balls with the diameter of 6.25mm and hexane as ball milling media, adding 8g of dispersant stearic acid and 160g of forming agent paraffin wax into a clean stainless steel ball milling tank, and then ball milling for 96h on a roller ball mill with the ball-material ratio of 10:1 and the ball milling rotation speed of 75 r/min. Taking out the wet ground material, drying in a vacuum drying oven at 80 ℃ for 4h, homogenizing and crushing, and sieving the powder by adopting a sieve with 200 meshes to prepare granules with certain components and particle size requirements.
(2) And (2) directly filling the mixture powder sieved in the step (1) into a die, pressing for 20s under the pressure of 350MPa, and preparing the uniformly mixed powder into a blank.
(3) And (3) putting the blank body pressed in the step (2) into a sintering furnace according to the working procedures of preheating, heating up, heat preservation and temperature control, heating up to 500 ℃ in vacuum degreasing, keeping the temperature for 80min, and controlling the temperature deviation to be +/-0.50 ℃.
(4) Solid-phase sintering stage: the heating temperature is increased from 500 ℃ to 1330 ℃, the heating rate is not more than 5 ℃/min, the heat preservation and temperature control time is 45min at the sintering temperature of 900 ℃, the heat preservation and temperature control time is 60min at 1220 ℃ and the heat preservation and temperature control time is 60min at 1330 ℃, and the temperature deviation is controlled to be +/-0.50 ℃;
liquid phase sintering stage: the heating temperature is increased from 1330 ℃ to 1470 ℃, the heating rate is set to be within 3 ℃/min, 5MPa of high-purity 99.9995 percent argon gas is introduced, the heat preservation and temperature control time period is set to be 90min when the sintering temperature is 1470 ℃, and the temperature deviation is controlled to be +/-0.50 ℃.
And (3) a cooling stage: slowly cooling to 1200 +/-0.5 ℃, rapidly cooling to room temperature, taking high-purity 99.9995% argon as a cooling medium, reaching the room temperature at a cooling rate of 36 ℃/min, discharging and taking out the metal ceramic alloy.
Example 3
Ti(C0.5,N0.5) Micron powder size FSSS1.2 weighing 760g, (Ti, W8, Mo5) (C)0.5,N0.5) Micron powder size FSSS1.5 weighing 240g, Ti (C)0.5,N0.5) Submicron powder particle size FSSS0.7 weighing 760g, (Ti, W8, Mo5) (C)0.5,N0.5) 240g of nano powder with the granularity of FSSS0.1, 200g of Ni powder with the granularity of FSSS1.5, 120g of Cr powder with the granularity of FSSS1.5, 650g of Co powder with the granularity of FSSS1.2, 600g of WC powder with the granularity of FSSS0.8 and 600g of Mo powder with the granularity of FSSS1.52C powder weighing 49g, powder size FSSS1.5 Cr2C3The powder weighed 60 g; 3500ml of ball milling medium hexane is weighed, 160g of forming agent is weighed by adopting paraffin, and 40g of dispersing agent is weighed by adopting stearic acid.
(1) Ball milling and mixing: putting the raw material powder prepared in the step (1) into YG6X alloy balls with the diameter of 8mm and hexane as ball milling media, adding 4g of dispersant stearic acid and 16g of forming agent paraffin wax into a clean stainless steel ball milling tank, and then ball milling for 72h on a roller ball mill, wherein the ball-to-material ratio is 11: 1, the ball milling rotating speed is 80 r/min. Taking out the wet ground material, drying in a vacuum drying oven at 80 ℃ for 4h, homogenizing and crushing, and sieving the powder by adopting a sieve with 150 meshes to prepare granules with certain components and particle size requirements.
(2) And (2) directly filling the mixture powder sieved in the step (1) into a die, pressing for 20s under the pressure of 150MPa, and preparing the uniformly mixed powder into a blank.
(3) And (3) putting the blank body pressed in the step (2) into a sintering furnace according to the working procedures of preheating, heating up, heat preservation and temperature control, heating up to 500 ℃ in vacuum degreasing, keeping the temperature for 90min, and controlling the temperature deviation to be +/-0.50 ℃.
(4) Solid-phase sintering stage: the heating temperature is increased from 500 ℃ to 1300 ℃, the heating rate is not more than 3 ℃/min, the heat preservation and temperature control time is 50min at the sintering temperature of 920 ℃, the heat preservation and temperature control time is 60min at 1270 ℃ and the heat preservation and temperature control time is 50min at 1350 ℃, and the temperature deviation is controlled to be +/-0.50 ℃;
liquid phase sintering stage: the heating temperature is increased from 1330 ℃ to 1430 ℃, the heating rate is set to be within 3 ℃/min, simultaneously 6MPa of high-purity 99.9995 percent argon gas is introduced, the heat preservation and temperature control time period is set to be 90min when the sintering temperature is 1450 ℃, and the temperature deviation is controlled to be +/-0.50 ℃.
And (3) a cooling stage: slowly cooling to 1200 +/-0.5 ℃, rapidly cooling to room temperature, taking out the cermet alloy after the cooling medium is high-purity 99.9995% argon reaching the room temperature at the cooling rate of 37 ℃/min.
Example 4
Ti(C0.5,N0.5) Micron powder size FSSS1.8 weigh 1000g, (Ti, W8, Mo5) (C)0.5,N0.5) Micron powder size FSSS1.5 weighing 120g, Ti (C)0.5,N0.5) Submicron powder particle size FSSS0.8 weigh 1080g, (Ti, W8, Mo5) (C)0.5,N0.5) 80g of Mo having a nanopowder particle size of FSSS0.05 and a powder particle size of FSSS1.52200g of C powder, 120g of Cr powder with the powder granularity of FSSS1.5, 580g of Co powder with the powder granularity of FSSS1.2, 380g of WC powder with the powder granularity of FSSS0.8 and Mo powder with the powder granularity of FSSS1.52The C powder weighed 320g, the TiN powder having a powder particle size of FSSS1.5 weighed 60g, and the TiC powder having a powder particle size of FSSS1.5 weighed 60 g. 3500ml of ball milling medium hexane is weighed, 160g of forming agent is weighed by adopting paraffin, and 20g of dispersing agent is weighed by adopting dodecylbenzene sulfonic acid.
(1) Ball milling and mixing: putting the raw material powder prepared in the step (1) into YG6X alloy balls with the diameter of 9mm and hexane as ball milling media, adding 20g of dispersing agent dodecylbenzene sulfonic acid and 200g of forming agent paraffin into a clean stainless steel ball milling tank, and then ball milling for 116h on a roller ball mill with the ball-material ratio of 13:1 and the ball milling rotation speed of 100 r/min. Taking out the wet ground material, drying in a vacuum drying oven at 80 ℃ for 4h, homogenizing and crushing, and sieving the powder by adopting a sieve with 250 meshes to prepare granules with certain components and particle size requirements.
(2) And (2) directly filling the mixture powder sieved in the step (1) into a die, pressing for 30s under the pressure of 200MPa, and preparing the uniformly mixed powder into a blank.
(3) And (3) putting the blank body pressed in the step (2) into a sintering furnace according to the working procedures of preheating, heating up, heat preservation and temperature control, heating up to the vacuum degreasing temperature of 600 ℃, keeping the temperature for 90min, and controlling the temperature deviation to be +/-0.50 ℃.
(4) Solid-phase sintering stage: the heating temperature is increased from 600 ℃ to 1300 ℃, the heating rate is not more than 5 ℃/min, the heat preservation and temperature control time is 70min at the sintering temperature of 920 ℃, the heat preservation and temperature control time is 60min at 1270 ℃ and the heat preservation and temperature control time is 50min at 1350 ℃, and the temperature deviation is controlled to be +/-0.50 ℃;
liquid phase sintering stage: the heating temperature is increased from 1330 ℃ to 1430 ℃, the heating rate is set to be within 4 ℃/min, 8MPa of high-purity 99.9995 percent argon gas is introduced, the heat preservation and temperature control time period is set to be 70min at the sintering temperature of 1460 ℃, and the temperature deviation is controlled to be +/-0.50 ℃.
And (3) a cooling stage: slowly cooling to 1200 +/-0.5 ℃, rapidly cooling to room temperature, wherein the cooling medium is high-purity 99.9995% argon, the cooling rate reaches the room temperature at 38 ℃/min, discharging and taking out the cermet alloy
Example 5
Ti(C0.5,N0.5) Micron powder size FSSS1.8 weigh 1200g, (Ti, W8, Mo5) (C)0.5,N0.5) Micron powder size FSSS1.8 weigh 120g, Ti (C)0.5,N0.5) Submicron powder particle size FSSS1.0 weighing 1000g, (Ti, W8, Mo5) (C)0.5,N0.5) 80g of Mo having a nanopowder particle size of FSSS0.05 and a powder particle size of FSSS1.52200g of C powder, 120g of TaC/NbC powder with the powder granularity of FSSS1.5, 580g of Co powder with the powder granularity of FSSS1.2, 380g of WC powder with the powder granularity of FSSS0.8, 20g of VC with the powder granularity of FSSS1.2 and 300g of Cr with the powder granularity of FSSS 1.2. 350ml of ball milling medium hexane is weighed, 160g of forming agent is weighed by using paraffin, and 40g of dispersing agent is weighed by using stearic acid.
(1) Ball milling and mixing: putting the raw material powder prepared in the step (1) into YG6X alloy balls with the diameter of 8mm and hexane as ball milling media, adding 40g of dispersant stearic acid and 160g of forming agent paraffin wax into a clean stainless steel ball milling tank, and then ball milling for 48 hours on a roller ball mill at the ball-material ratio of 15:1 and the ball milling rotation speed of 120 r/min. Taking out the wet ground material, drying in a vacuum drying oven at 80 ℃ for 4h, homogenizing and crushing, and sieving the powder by adopting a sieve with 250 meshes to prepare granules with certain components and particle size requirements.
(2) And (2) directly filling the mixture powder sieved in the step (1) into a die, pressing for 300s under the pressure of 150MPa, and preparing the uniformly mixed powder into a blank.
(3) And (3) putting the blank body pressed in the step (2) into a sintering furnace according to the working procedures of preheating, heating up, heat preservation and temperature control, heating up to 800 ℃ in vacuum degreasing, keeping the temperature for 90min, and controlling the temperature deviation to be +/-0.50 ℃.
(4) Solid-phase sintering stage: the heating temperature is increased from 800 ℃ to 1300 ℃, the heating rate is not more than 5 ℃/min, the heat preservation and temperature control time is 50min at the sintering temperature of 920 ℃, the heat preservation and temperature control time is 50min at the temperature of 1270 ℃ and the heat preservation and temperature control time is 50min at the temperature of 1350 ℃, and the temperature deviation is controlled to be +/-0.50 ℃;
liquid phase sintering stage: the heating temperature is increased from 1330 ℃ to 1430 ℃, the heating rate is set to be within 2 ℃/min, meanwhile, 10MPa of high-purity 99.9998 percent argon gas is introduced, the heat preservation and temperature control time period is set to be 80min when the sintering temperature is 1430 ℃, and the temperature deviation is controlled to be +/-0.50 ℃.
And (3) a cooling stage: slowly cooling to 1200 +/-0.5 ℃, rapidly cooling to room temperature, taking high-purity 99.9998% argon as a cooling medium, reaching the room temperature at a cooling rate of 40 ℃/min, discharging and taking out the metal ceramic alloy.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and the scope of the present invention is defined by the appended claims, and all changes that come within the meaning and range of equivalency of the specification are therefore intended to be embraced therein.
Claims (10)
1. The coreless-ring structure metal ceramic alloy is characterized by comprising, by weight, 10-55% of Ti (C, N) micron powder, 10-55% of (Ti, M) (C, N) micron powder, 10-55% of Ti (C, N) submicron or/and nano powder, 10-55% of (Ti, M) (C, N) submicron or/and nano powder, 5-20% of WC (wolfram carbide), 0-30% of TiC, 0-30% of TiN, 0-20% of Co, 0-20% of Ni, 0-10% of Cr, 0-15% of MoC, 0-10% of TaC/NbC, 0-2% of VC, 0-5% of CrC and 0-1.2% of carbon black; wherein, the M element in the (Ti, M) (C, N) micron powder and the (Ti, M) (C, N) submicron or/and nanometer powder is any one or more of Mo, W, Ta, Nb, Zr, Cr and V solid solution powder; and C and N in the Ti (C, N), (Ti, M) (C, N) micron powder and the Ti (C, N), (Ti, M) (C, N) submicron or/and nanoscale powder adopt one of C/N atomic ratios 7/3, 6/4 or 5/5.
2. The cermet alloy with a coreless-ring structure as claimed in claim 1, wherein the composition comprises, in weight%, 15-45% of Ti (C, N), 15-45% of (Ti, M) (C, N) micropowder, 6-15% of Ti (C, N) micropowder and/or nanopowder, 7-15% of (Ti, M) (C, N) submicron or/and nanopowder, 12-18% of WC, 0.5-15% of TiC, 0.5-15% of TiN, 8-15% of Co, 3-8% of Ni, 1-5% of Cr, 5-12% of MoC, 2-10% of TaC/NbC, 0.3-1.0% of VC, 0.5-1.2% of CrC, 0.0-1.0% of carbon black.
3. The preparation method of the coreless-ring structure metal ceramic alloy is characterized by comprising the following steps of: (1) weighing the raw materials in the claim 1 or 2 according to a proportion, mixing, adding a grinding medium, a dispersing agent and a forming agent, and uniformly mixing to obtain a prepared raw material; (2) the preparation raw materials are put into a grinding hard alloy ball milling tank of a ball mill and are ball milled to obtain a mixed material; (3) sieving the mixed material by a 150-250 mesh sieve or spray granulating; (4) directly filling the sieved mixed material into a mold and pressing into a blank; (5) firstly, the compression molding blank is put into a high vacuum degreasing positive pressure sintering rapid cooling furnace, gas in the furnace body is pumped out to ensure that the furnace body is vacuum and the vacuum degree is not more than 15Pa, then a sintering furnace power supply is started, the heating degreasing stage, the solid phase sintering stage, the liquid phase sintering stage and the rapid cooling stage are sequentially carried out, and then the metal ceramic alloy is taken out of the furnace and taken out.
4. The method according to claim 3, wherein the grinding medium in the step (1) is hexane or absolute ethyl alcohol, and the mass fraction of the hexane or absolute ethyl alcohol in the total amount of the grinding medium is 0.5-1.8%; the dispersing agent is dodecyl benzene sulfonic acid, stearic acid or ethoprofen, and the mass fraction of the dispersing agent is 0.1-0.5%; the forming agent is one or more of gasoline and rubber, paraffin, polyvinyl alcohol, synthetic rubber, ethylene glycol or SBS (styrene butadiene styrene) which are used as solutes, and the mass fraction of the forming agent is 2-5%.
5. The method according to claim 3, wherein the ball mill in the step (2) is a rolling ball mill or a planetary ball mill, the cemented carbide balls have a ball diameter of 6.25-10 mm and a ball-to-material ratio of 8-15: l; the ball milling speed of the ball mill is 70-120 r/min, and the ball milling time is 48-144 h.
6. The method according to claim 3, wherein in the step (4), the pressure in the mold is 150 to 450MPa, and the dwell time is 15 to 300 s.
7. The method according to claim 3, wherein the heating and degreasing process is carried out according to the procedures of preheating, gas introduction, temperature rise, heat preservation and temperature control, the heating and vacuum degreasing temperature is raised to 450-800 ℃, and then the heat preservation is carried out for 50-100 min.
8. The method according to claim 3, wherein the heating temperature in the solid phase sintering stage is increased from 450-800 ℃ to 1280-1350 ℃, the heating rate is not more than 5 ℃/min, and the temperature is respectively maintained for 45-90 min when the sintering temperature reaches a certain temperature in the range of 850-950 ℃, 1220-1280 ℃ and 1280-1350 ℃.
9. The method according to claim 3, wherein when the solid phase sintering stage is completed and then the liquid phase sintering stage is carried out, the temperature is raised to 1430-1470 ℃ at the temperature rise rate of 2-5 ℃/min, the heat preservation time of the liquid phase sintering stage is 45-90 min, and meanwhile 1-10 MPa of argon gas is introduced, and the purity of the argon gas is more than 99.995%.
10. The method as claimed in claim 3, wherein the liquid phase sintering step is followed by a rapid cooling step, wherein the temperature is slowly cooled to 1200 ℃, argon gas is introduced as a cooling medium to rapidly cool the liquid phase sintering step to room temperature, the purity of the argon gas is greater than 99.995%, and the cooling rate is greater than 35 ℃/min to reach room temperature.
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