CN111218599B - TiB2Preparation method of-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material - Google Patents
TiB2Preparation method of-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 86
- 238000005260 corrosion Methods 0.000 title claims abstract description 86
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000919 ceramic Substances 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 160
- 229910033181 TiB2 Inorganic materials 0.000 claims abstract description 56
- 238000000498 ball milling Methods 0.000 claims abstract description 51
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000011812 mixed powder Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 238000005520 cutting process Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000011195 cermet Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010892 electric spark Methods 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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- 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
- C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- 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
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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Abstract
The invention discloses a TiB2The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material comprises the following steps of 1: weighing raw materials and carrying out ball milling; the raw material comprises TiB2Powder, WC powder, Co powder, Ni powder, Cr powder, Fe powder and Ti powder; putting the raw materials into a ball mill for ball milling; step 2: a drying step; putting the ball-milled powder into a vacuum drying box for drying; and step 3: sintering; and (4) performing spark plasma sintering on the dried mixed powder. The method is easy to implement, and the TiB prepared by the method2the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material has excellent aluminum corrosion resistance.
Description
Technical Field
The invention belongs to the field of aluminum liquid corrosion resistant materials, and particularly relates to a TiB2A preparation method of-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material.
Background
At present, aluminum and its alloy are widely used in the fields of traffic, energy, electronics, etc. But the aluminum liquid is one of the most corrosive metal liquids, so that equipment directly contacting the aluminum liquid is greatly corroded in a smelting, casting and hot-dip aluminizing production line, and the service life of the equipment is greatly shortened. And the dissolution of the materials in the aluminum liquid may pollute the aluminum liquid, so that the product quality is low, and the production efficiency is influenced. In a hot-dip aluminum plating production line, equipment such as an aluminum liquid bearing tank, an immersion roller and the like needs to be soaked in aluminum liquid for a long time, so that the service life of the hot-dip aluminum plating production equipment is shortened, the quality of a plating layer is reduced, the energy consumption is increased, the production efficiency is reduced and the like. Therefore, the aluminum liquid corrosion resistance of the material is improved, and a series of corrosion problems such as aluminum liquid pollution, corrosion perforation of an aluminum liquid containing container, aluminum sticking of an aluminum forming die and the like can be effectively solved. TiB2As the only stable compound of transition metal elements Ti and B, the compound has a close-packed hexagonal C32 crystal structure, and has high hardness, high wear resistance and good high-resistanceAnd (4) warm oxidation performance. But TiB2Poor high-temperature toughness, low diffusion coefficient and poor sintering property, so that the pure TiB2Sintering preparation of the material is difficult. Therefore, the characteristics of excellent toughness and low melting point of the metal binding phase can be utilized to improve TiB2Poor toughness and difficult sintering. But TiB2The wettability with most metals is poor, so that it is necessary to select a metal having good wettability with the metal as a binder phase.
Therefore, it is necessary to design a new preparation method of the molten aluminum corrosion resistant material.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a TiB2Preparation method of-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material, the method is easy to implement, and TiB prepared by the method2the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material has excellent aluminum corrosion resistance.
The technical solution of the invention is as follows:
TiB2The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material comprises the following steps:
step 1: weighing raw materials and ball-milling
The raw material comprises TiB2Powder, WC powder, Co powder, Ni powder, Cr powder, Fe powder and Ti powder;
putting the raw materials into a ball mill for ball milling;
step 2: drying step
Putting the ball-milled powder into a vacuum drying box for drying;
and step 3: sintering step
And (4) performing spark plasma sintering on the dried mixed powder.
The raw materials comprise the following components in percentage by mass:
TiB2powder: 70-88%, WC powder: 1% -2%, Co powder: 2.15-6.03%, Ni powder: 2.15-6.03%, Cr powder: 1.90-5.31%, Fe powder: 2.04-5.72%, Ti powder: 1.76 to 4.91 percent.
The purity of the WC powder, the Co powder, the Ni powder, the Cr powder, the Fe powder and the Ti powder is more than or equal to 99.9 percent, and the granularity is less than or equal to 15 microns.
TiB2The purity of the powder is more than or equal to 99.5 percent, and the particle size is less than or equal to 35 microns.
The ball milling is wet ball milling, and absolute ethyl alcohol is used as a ball milling medium.
In the ball milling process, the ball: the mixed powder ratio is 3:1-5:1, the rotating speed is 200-300r/min, the ball milling time is 1-3 hours, and the mixture refers to the mixture of WC powder, Co powder, Ni powder, Cr powder, Fe powder and Ti powder. The ball-to-feed ratio is a mass ratio.
In the drying process, the drying temperature is 70-90 ℃, the vacuum degree is-0.1 to-0.09 MPa, and the drying is carried out for 8-12 hours.
Sintering refers to spark plasma sintering.
And (3) placing the dried mixed powder in a graphite mold, heating to T at the temperature rise rate of 300 ℃/min in the temperature range of 200-.
The mass content of each component is as follows: TiB2:88%,WC:2%,Co:2.15%,Ni:2.15%,Cr:1.90%,Fe: 2.04%,Ti:1.76%。
Preparation of the obtained TiB2the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material comprises the following components in percentage by mass:
TiB2:70-88%,WC:1%-2%,Co:2.15-6.03%,Ni:2.15-6.03%,Cr:1.90-5.31%,Fe: 2.04-5.72%,Ti:1.76-4.91%。
TiB2the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material is prepared by ball milling, drying and sintering raw materials;
the raw materials and the mass percentage ratio are as follows:
TiB2powder: 70-88%, WC powder: 1% -2%, Co powder: 2.15-6.03%, Ni powder: 2.15-6.03%, Cr powder: 1.90-5.31%, Fe powder: 2.04-5.72%, Ti powder: 1.76 to 4.91 percent.
TiB2Has a plurality of excellent properties such as high hardness, high wear resistance, good high-temperature oxidation resistance and the likeCan be used. But TiB2Poor high-temperature toughness, low diffusion coefficient and poor sintering property, so that the pure TiB2Sintering preparation of the material is difficult. Therefore, the characteristics of excellent toughness and low melting point of the metal binding phase can be utilized to improve TiB2Poor toughness and difficult sintering. But TiB2The wettability with most metals is poor, so it is necessary to select one with TiB2The metal with good wettability is used as a binding phase. The applicant found only Fe, Co, Ni and TiB through creative work2Has better wettability, so the elements Fe, Co and Ni are selectively added to improve the TiB2The addition of Cr element has very good strengthening effect, and Fe and Ni are easy to TiB at high temperature2The brittle secondary boride is generated, and the addition of Ti element can prevent the brittle secondary boride from being generated in the sintering process and improve the mechanical property of the material. The WC has excellent corrosion resistance, and a small amount of WC can play a role in enhancing the corrosion resistance of the material.
Advantageous effects
The invention uses TiB2The material comprises the following raw materials of powder, WC powder (tungsten carbide powder), Co powder, Ni powder, Cr powder, Fe powder and Ti powder in percentage by mass: TiB270-88% of powder, 2% of WC powder, 2.15-6.03% of Co powder, 2.15-6.03% of Ni powder, 1.90-5.31% of Cr powder, 2.04-5.72% of Fe powder and 1.76-4.91% of Ti powder. Mixing said TiB2After the powder, WC powder, Co powder, Ni powder, Cr powder, Fe powder and Ti powder are mixed according to the proportion, the mixture is ball-milled, dried and sintered by discharge plasma to prepare TiB2A base cermet material. The invention passes through TiB2The ceramic powder is added with metal simple substance as a binding phase, thereby obviously reducing TiB2The sintering temperature of the alloy improves TiB2Sintering property of (2). And compared with the traditional sintering process, the spark plasma sintering process has great advantages, can obviously reduce the sintering temperature and the sintering time, and has the characteristics of low temperature, rapidness and high efficiency. Meanwhile, the preparation process is simple, the price is low, the excellent corrosion resistance is shown in the aluminum liquid, and the preparation method has important application value in industry.
The present invention designs a new goldThe system is a binding phase to improve TiB2The material has the defect of difficult sintering, has excellent aluminum liquid corrosion resistance, low price, simple preparation process and considerable industrial application prospect.
The invention has the following characteristics:
(1) the invention passes through TiB2The material is added with Fe, Co, Cr, Ni and Ti metal elementary powder and WC powder, and is sintered by discharge plasma at a lower sintering temperature to obtain an integral material.
(2) Compared with the common pressureless sintering and hot-pressing sintering, the sintering process adopts the spark plasma sintering process, and can obtain compact materials at lower sintering temperature. And the spark plasma sintering greatly shortens the sintering time, improves the production efficiency, reduces the production cost and improves the density of the metal ceramic composite material.
(3) The metal ceramic integral material has the characteristics of excellent corrosion resistance, good high-temperature stability, simple preparation process, low cost and the like in molten aluminum, and has important practical value in the aluminum industry of hot-dip aluminum plating and the like.
Drawings
FIG. 1 shows TiB in the first embodiment of the present invention2SEM image of the mixed powder of-WC-Fe-Co-Ni-Cr-Ti after ball milling.
FIG. 2 shows TiB prepared in the first embodiment of the present invention2-microscopic SEM image of WC-Fe-Co-Ni-Cr-Ti cermet monolith.
FIG. 3 shows TiB prepared in the second embodiment of the present invention2-microscopic SEM image of WC-Fe-Co-Ni-Cr-Ti cermet monolith.
FIG. 4 shows TiB prepared in the third embodiment of the present invention2-microscopic SEM image of WC-Fe-Co-Ni-Cr-Ti cermet monolith.
FIG. 5 is a graph of etch depth versus time for three different materials in an embodiment of the present invention.
FIG. 6 is an SEM image of the corrosion interface of the material after 4, 6, 8 and 10 days of corrosion in molten aluminum at 700 ℃ in one embodiment of the invention, wherein FIGS. 6(a) to 6(d) are SEM images of the corrosion interface after 4, 6, 8 and 10 days of corrosion respectively.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the following specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The preparation method comprises the following steps: weighing TiB2The material is prepared by mixing and ball-milling the powder, WC powder, Co powder, Ni powder, Cr powder, Fe powder and Ti powder according to the mass percentage, and then carrying out vacuum drying and spark plasma sintering. The method comprises the following steps:
(1) weighing the following powder in percentage by mass:
TiB2:70-88%,WC:1%-2%,Co:2.15-6.03%,Ni:2.15-6.03%,Cr:1.90-5.31%,Fe: 2.04-5.72%,Ti:1.76-4.91%。
and mixing the weighed powders to obtain mixed powder.
(2) Pouring the mixed powder into a ball milling tank, adding grinding balls according to the ball material ratio of 5:1, adding a proper amount of absolute ethyl alcohol, and adopting a wet ball milling process. The rotating speed of the ball mill is 300r/min, and the ball milling time is 3 hours.
(3) And (3) drying the powder subjected to ball milling in a vacuum drying oven at the drying temperature of 70-90 ℃ under the vacuum degree of-0.1 MPa for 12 hours.
(4) Taking out the dried powder, putting the dried powder into a cylindrical graphite die, and then sintering by discharge plasma to obtain the integral material, wherein the sintering process comprises the following steps: heating to 1300 deg.C at a heating rate of 300 deg.C/min, and maintaining at 1300 deg.C for 5 min under 50-60 MPa.
The monolithic material obtained by the above steps is in the shape of a cylindrical block. In order to research the aluminum liquid corrosion resistance, a corrosion experiment is carried out on the aluminum liquid corrosion resistance, and the preparation of a sample of the corrosion experiment is carried out according to the following method: the obtained cylindrical block was cut into rectangular parallelepiped test pieces of 4X 5X 10mm using a spark numerically controlled wire cutter, the cutting position being preferably the center position of the sample. Then placing the aluminum alloy into 700 ℃ aluminum liquid for corrosion experiment.
The first embodiment is as follows:
TiB2The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material comprises the following steps: preparing a sample: mixing TiB2WC, Fe, Co, Ni, Cr and Ti powder are weighed according to the following mass percent: TiB288% of powder, 2% of WC powder, 2.15% of Co powder, 2.15% of Ni powder, 1.90% of Cr powder, 2.04% of Fe powder and 1.76% of Ti powder. The TiB2The purity of the powder is 99.5 percent, and the particle size is less than 35 microns; the purity of the WC powder, the Co powder, the Ni powder, the Cr powder, the Fe powder and the Ti powder is more than 99.9 percent, and the granularity is less than 15 microns.
(2) Ball milling: putting the weighed mixture into a ball milling tank, and mixing the mixture according to a ball-to-mixture mass ratio of 5: and 1, weighing the required balls and putting the balls into a ball milling tank. And (3) adopting a wet ball milling process, and pouring a proper amount of absolute ethyl alcohol into the ball milling tank to cover the powder. The rotating speed of the ball mill is 300r/min, the ball milling time is 3 hours, the machine is stopped and is rested for 15 minutes every 2 hours, and then the ball milling is carried out. FIG. 1 is an SEM image of the mixed powder after ball milling. It can be seen from the figure that after the ball milling of the mixed powder, the metal powder is uniformly dispersed in the TiB2In the powder.
(3) And (3) drying: and (3) putting the mixed slurry subjected to ball milling into a vacuum drying oven for drying, wherein the temperature of the drying oven is 90 ℃, the vacuum degree is-0.1 MPa, and the drying time is 12 hours. The dried powder was taken out for further use.
(4) And (3) sintering: the sintering equipment used in this example was spark plasma sintering, and the dried powder was placed in a cylindrical graphite mold and then sintered in the sintering equipment, and the sintering process was set as follows: heating from room temperature to 1300 deg.C at a heating rate of 300 deg.C/min, maintaining at 1300 deg.C for 5 min, and pressurizing at 60MPa during sintering. And cooling along with the furnace after sintering is finished, and then demoulding to obtain a sample. FIG. 2 is a microscopic topography of a sample under a Scanning Electron Microscope (SEM).
And cutting the prepared sample into cuboid samples with the size of 4 multiplied by 5 multiplied by 10mm by using an electric spark numerical control wire cutting machine, and cutting 5 samples, wherein the cutting position is preferably the central position of the sample. And (4) polishing the surface of the sample by using sand paper, and removing an oxide film on the surface of the sample. And then measuring the thickness of the sample before corrosion by using a micrometer, then putting the sample into a graphite crucible filled with aluminum liquid at 700 ℃ for a corrosion experiment, heating and preserving heat by using a well-type resistance furnace, respectively corroding for 2 days, 4 days, 6 days, 8 days and 10 days, then taking out, analyzing the texture of a corrosion interface by using a Scanning Electron Microscope (SEM), and measuring the phased chemical components by using an energy spectrometer (EDS).
The corrosion depth and the corrosion rate of the sample at different time are calculated, the corrosion rate is measured by using a depth method in the experiment, and the calculation formula is as follows: v ═ a-b)/2 t.
And a is the thickness of the sample before corrosion, b is the thickness of the sample after corrosion, t is corrosion time, the thickness a before corrosion is accurately measured by a micrometer before a corrosion experiment, then the structural observation is carried out on the cross section of the sample after corrosion under a scanning electron microscope, and the residual thickness b of the sample after corrosion is measured by Smile View software.
Example two:
TiB2The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material comprises the following steps:
(1) sample preparation: mixing TiB2WC, Fe, Co, Ni, Cr and Ti powder are weighed according to the following mass percent: TiB280% of powder, 2% of WC powder, 3.87% of Co powder, 3.87% of Ni powder, 3.43% of Cr powder, 3.68% of Fe powder and 3.15% of Ti powder.
The TiB2The purity of the powder is 99.5 percent, and the particle size is less than 35 microns; the purity of the WC powder, the Co powder, the Ni powder, the Cr powder, the Fe powder and the Ti powder is more than 99.9 percent, and the granularity is less than 15 microns.
(2) Ball milling: putting the weighed mixture into a ball milling tank, and mixing the mixture according to a ball-to-mixture mass ratio of 4: and 1, weighing the required balls and putting the balls into a ball milling tank. MiningAnd (3) performing a wet ball milling process, and pouring a proper amount of absolute ethyl alcohol into the ball milling tank to cover the powder. The rotating speed of the ball mill is 250r/min, the ball milling time is 2 hours, wherein the ball mill is stopped and rested for 15 minutes every 1 hour, and then the ball milling is carried out. FIG. 1 is an SEM image of the mixed powder after ball milling. It can be seen from the figure that after the ball milling of the mixed powder, the metal powder is uniformly dispersed in the TiB2In the powder.
(3) And (3) drying: and (3) putting the mixed slurry subjected to ball milling into a vacuum drying oven for drying, wherein the temperature of the drying oven is 80 ℃, the vacuum degree is 0.09MPa, and the drying time is 10 hours. The dried powder was taken out for further use.
(4) And (3) sintering: the sintering equipment used in this example was spark plasma sintering, and the dried powder was placed in a cylindrical graphite mold and then sintered in the sintering equipment, and the sintering process was set as follows: the temperature is raised from room temperature to 1400 ℃ at a heating rate of 200 ℃/min, the temperature is kept at 1400 ℃ for 10 minutes, and the pressure is increased by 50MPa in the sintering process. And cooling along with the furnace after sintering is finished, and then demoulding to obtain a sample.
And cutting the prepared sample into cuboid samples with the size of 4 multiplied by 5 multiplied by 10mm by using an electric spark numerical control wire cutting machine, and cutting 5 samples, wherein the cutting position is preferably the central position of the sample. And (4) polishing the surface of the sample by using sand paper, and removing an oxide film on the surface of the sample. And then measuring the thickness of the sample before corrosion by using a micrometer, then putting the sample into a graphite crucible filled with aluminum liquid at 700 ℃ for a corrosion experiment, heating and preserving heat by using a well-type resistance furnace, respectively corroding for 2 days, 4 days, 6 days, 8 days and 10 days, then taking out, analyzing the texture of a corrosion interface by using a Scanning Electron Microscope (SEM), and measuring the phased chemical components by using an energy spectrometer (EDS).
The corrosion depth and the corrosion rate of the sample at different time are calculated, the corrosion rate is measured by using a depth method in the experiment, and the calculation formula is as follows: v ═ a-b)/2 t.
And a is the thickness of the sample before corrosion, b is the thickness of the sample after corrosion, t is corrosion time, the thickness a before corrosion is accurately measured by a micrometer before a corrosion experiment, then the structural observation is carried out on the cross section of the sample after corrosion under a scanning electron microscope, and the residual thickness b of the sample after corrosion is measured by Smile View software.
FIG. 3 shows the microscopic morphology of the sample under a scanning electron microscope.
Example three:
TiB2The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material comprises the following steps:
(1) sample preparation: mixing TiB2WC, Fe, Co, Ni, Cr and Ti powder are weighed according to the following mass percent: TiB270% of powder, 2% of WC powder, 6.03% of Co powder, 6.03% of Ni powder, 5.31% of Cr powder, 5.72% of Fe powder and 4.91% of Ti powder.
The TiB2The purity of the powder is 99.5 percent, and the particle size is less than 35 microns; the purity of the WC powder, the Co powder, the Ni powder, the Cr powder, the Fe powder and the Ti powder is more than 99.9 percent, and the granularity is less than 15 microns.
(2) Ball milling: and (3) putting the weighed mixture into a ball milling tank, and weighing the required balls and putting the balls into the ball milling tank according to the mass ratio of the balls to the mixture of 3: 1. And (3) adopting a wet ball milling process, and pouring a proper amount of absolute ethyl alcohol into the ball milling tank to cover the powder. The rotating speed of the ball mill is 200r/min, and the ball milling time is 1 hour. FIG. 1 is an SEM image of the mixed powder after ball milling. It can be seen from the figure that after the ball milling of the mixed powder, the metal powder is uniformly dispersed in the TiB2In the powder.
(3) And (3) drying: and (3) putting the mixed slurry subjected to ball milling into a vacuum drying oven for drying, wherein the temperature of the drying oven is 70 ℃, the vacuum degree is 0.095MPa, and the drying time is 8 hours. The dried powder was taken out for further use.
(4) And (3) sintering: the sintering equipment used in this example was spark plasma sintering, and the dried powder was placed in a cylindrical graphite mold and then sintered in the sintering equipment, and the sintering process was set as follows: the temperature is increased from room temperature to 1350 ℃ at the heating rate of 250 ℃/min, the temperature is kept at 1350 ℃ for 5 minutes, and the pressure is increased to 55MPa in the sintering process. And cooling along with the furnace after sintering is finished, and then demoulding to obtain a sample.
And cutting the prepared sample into cuboid samples with the size of 4 multiplied by 5 multiplied by 10mm by using an electric spark numerical control wire cutting machine, and cutting 5 samples, wherein the cutting position is preferably the central position of the sample. And (4) polishing the surface of the sample by using sand paper, and removing an oxide film on the surface of the sample. And then measuring the thickness of the sample before corrosion by using a micrometer, then putting the sample into a graphite crucible filled with aluminum liquid at 700 ℃ for a corrosion experiment, heating and preserving heat by using a well-type resistance furnace, respectively corroding for 2 days, 4 days, 6 days, 8 days and 10 days, then taking out, analyzing the texture of a corrosion interface by using a Scanning Electron Microscope (SEM), and measuring the phased chemical components by using an energy spectrometer (EDS).
The corrosion depth and the corrosion rate of the sample at different time are calculated, the corrosion rate is measured by using a depth method in the experiment, and the calculation formula is as follows: v ═ a-b)/2 t.
And a is the thickness of the sample before corrosion, b is the thickness of the sample after corrosion, t is corrosion time, the thickness a before corrosion is accurately measured by a micrometer before a corrosion experiment, then the structural observation is carried out on the cross section of the sample after corrosion under a scanning electron microscope, and the residual thickness b of the sample after corrosion is measured by Smile View software.
FIG. 4 shows the microscopic morphology of the sample under a scanning electron microscope.
FIG. 5 is a graph of etch depth versus time for three different materials in the examples. It can be seen from the figure that the etch depth of this material increases with the time of etching, but the etch rate decreases with time. The average corrosion rate of the cermet material in the first example was calculated as: 1.12X 10-3mm/h; the average corrosion rate of the cermet material in example two was: 1.95X 10-3mm/h; the average corrosion rate of the cermet material in example three was: 8.42X 10-3mm/h. Compared with the corrosion rate of cast iron in molten aluminum of 0.85mm/h, the corrosion rate of the material to molten aluminum is greatly improved, and the material in the first embodiment has the best molten aluminum corrosion resistance.
FIG. 6 is an SEM image of a corrosion interface of the material after 4, 6, 8 and 10 days of corrosion in molten aluminum at 700 ℃ in the first embodiment. As can be seen from the figure, the existence of the gap between the aluminum liquid and the material in the early stage of corrosion results in poor wettability of the aluminum liquid and the material, and the aluminum liquid and the base material are wetted along with the increase of the corrosion time, and are tightly combined.
The embodiments are only for the purpose of facilitating understanding of the technical solutions of the present invention, and do not constitute a limitation to the scope of the present invention, and any simple modification, equivalent change and modification made to the above solutions without departing from the contents of the technical solutions of the present invention or the technical spirit of the present invention still fall within the scope of the present invention.
Claims (3)
1. TiB2The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material is characterized by comprising the following steps of:
step 1: weighing raw materials and ball-milling
The raw material comprises TiB2Powder, WC powder, Co powder, Ni powder, Cr powder, Fe powder and Ti powder;
putting the raw materials into a ball mill for ball milling;
step 2: drying step
Putting the ball-milled powder into a vacuum drying box for drying;
and step 3: sintering step
Performing spark plasma sintering on the dried mixed powder;
the raw materials comprise the following components in percentage by mass:
TiB2powder: 70-88%, WC powder: 1-2%, Co powder: 2.15-6.03%, Ni powder: 2.15-6.03%, Cr powder: 1.90-5.31%, Fe powder: 2.04-5.72%, Ti powder: 1.76 to 4.91 percent;
the specific process of spark plasma sintering is as follows: the dried mixed powder is arranged in a graphite mould, the temperature is raised to T at the temperature raising rate of 300 ℃/min with temperature of 200-;
the purity of the WC powder, the Co powder, the Ni powder, the Cr powder, the Fe powder and the Ti powder is more than or equal to 99.9 percent, and the granularity is less than or equal to 15 microns;
the TiB2The purity of the powder is more than or equal to 99.5 percent, and the particle size is less than or equal to 35 microns;
in the ball milling process, the ball: the mixing powder ratio is 3:1-5:1, the rotating speed is 200-.
2. The TiB of claim 12The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material is characterized in that the ball milling is wet ball milling, and absolute ethyl alcohol is used as a ball milling medium.
3. TiB according to claim 1 or 22The preparation method of the-WC-Fe-Co-Ni-Cr-Ti aluminum liquid corrosion resistant metal ceramic integral material is characterized in that the mass content of each component is as follows: TiB2:88%,WC:2%,Co:2.15%,Ni:2.15%,Cr:1.90%,Fe:2.04%,Ti:1.76%。
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JP2005213605A (en) * | 2004-01-30 | 2005-08-11 | Tocalo Co Ltd | Composite material, thermally sprayed film coated member and method for manufacturing the member |
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