CN115108582A - Preparation method of titanium pentoxide coating material - Google Patents
Preparation method of titanium pentoxide coating material Download PDFInfo
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- CN115108582A CN115108582A CN202210878942.4A CN202210878942A CN115108582A CN 115108582 A CN115108582 A CN 115108582A CN 202210878942 A CN202210878942 A CN 202210878942A CN 115108582 A CN115108582 A CN 115108582A
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- 239000000463 material Substances 0.000 title claims abstract description 89
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 title claims abstract description 66
- AZCUJQOIQYJWQJ-UHFFFAOYSA-N oxygen(2-) titanium(4+) trihydrate Chemical compound [O-2].[O-2].[Ti+4].O.O.O AZCUJQOIQYJWQJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 73
- 238000000498 ball milling Methods 0.000 claims abstract description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000011812 mixed powder Substances 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002245 particle Substances 0.000 abstract description 9
- 238000001704 evaporation Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 1
- -1 TiO and TiO 2 Chemical compound 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/043—Titanium sub-oxides
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a preparation method of a titanium pentoxide coating material, which comprises the following steps: (1) mixing titanium powder and titanium dioxide powder, and carrying out first ball milling to obtain mixed powder; (2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) to obtain a pressed blank; (3) sequentially pre-burning and carrying out second ball milling on the green compacts obtained in the step (2) to obtain pre-burned materials; (4) and (4) sintering the pre-sintered material obtained in the step (3) to obtain the titanium pentoxide coating material. The preparation method provided by the invention can effectively control the particle size of the titanium pentoxide coating material and improve the density and uniformity of the coating material.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a preparation method of a titanium pentoxide coating material.
Background
The vacuum coating is mainly classified into three types, i.e., evaporation coating, sputtering coating, ion plating, and the like. Vapor deposition is the deposition of a substance onto a solid surface by heating the substance. Evaporating substances such as metal and compound are placed in a crucible or hung on a hot wire to be used as an evaporation source, workpieces to be plated such as metal, ceramic, plastic and other substrates are placed in front of the crucible, and after the system is pumped to high vacuum, the crucible is heated to evaporate the substances in the crucible. Atoms or molecules of the evaporation material are deposited on the substrate surface in a condensed manner, and the thickness of the thin film depends on the evaporation rate and time of the evaporation source and is related to the distance between the evaporation source and the substrate. For large-area coating, a mode of rotating a substrate or multiple evaporation sources is often adopted to ensure the uniformity of the thickness of the film layer.
Titanium oxide (Ti) 3 O 5 ) Is a high-refractive index material with excellent properties for visible infrared spectrum, has a melting point of 1780 ℃, and is widely used for depositing TiO in the field of optical coating 2 A film. TiO 2 2 The coating material of the film is various, and the film can be formed from metal titanium to titanium oxide, including TiO and TiO 2 、Ti 2 O 3 、Ti 3 O 5 And Ti 4 O 7 Etc. are used. Studies have shown that when Ti is used 3 O 5 When the coating material is used as a coating material, the coating material has good recycling property and stability, and the film refractive index is excellent.
CN113213915A discloses a preparation method of a low-temperature titanium pentoxide crystal coating material, which comprises the steps of pressing a mixed raw material into a blank by a cold isostatic pressing process and placing the blank into a crucible; putting the crucible into a furnace body, vacuumizing the furnace body, and starting heating the furnace body; and (3) preparing low-temperature titanium pentoxide crystal particles with preset specifications by adopting a sectional heating mode and controlling the reaction temperature and the reaction time of each section.
CN101333003B discloses a preparation method of a titanium pentoxide coating material, which adopts a vacuum induction heating method to prepare the titanium pentoxide coating material, and comprises the steps of preparing a titanium pentoxide tea color sheet by vacuum induction heating and preparing a titanium pentoxide crystal by vacuum induction heating.
The above method can prepare Ti 3 O 5 Coating material, but preparing the resultant Ti 3 O 5 The coating material generally has the problems of uneven granularity, low purity, low density and the like, the performance of a sputtered film is seriously influenced, and the requirement of high-end optical coating industry on the evaporation coating material cannot be met.
Thus, Ti having high purity and compactness and uniform particle size is provided 3 O 5 The preparation method of the coating material has important significance.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of a titanium pentoxide coating material, and compared with the prior art, the preparation method provided by the invention can obtain Ti with high purity and density and uniform particle size 3 O 5 The coating material can effectively improve the performance of the vapor deposition film.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a titanium pentoxide coating material, which comprises the following steps:
(1) mixing titanium powder and titanium dioxide powder, and carrying out first ball milling to obtain mixed powder;
(2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) to obtain a pressed blank;
(3) sequentially pre-burning and carrying out second ball milling on the green compacts obtained in the step (2) to obtain pre-burned materials;
(4) and (4) sintering the pre-sintered material obtained in the step (3) to obtain the titanium pentoxide coating material.
The preparation method provided by the invention comprises the steps of firstly, fully mixing titanium powder and titanium dioxide powder through first ball milling, cold isostatic pressing and presintering treatment to preliminarily generate the trititanium pentoxide, then, carrying out second ball milling to grind the obtained trititanium pentoxide into fine crystal nuclei, and then, regulating the temperature and the pressure in the sintering process to grow the crystal nuclei and control the particle size of the crystal nuclei, thereby finally obtaining the trititanium pentoxide evaporation particles with good density and uniform particle size.
In the invention, the grain size distribution of the titanium pentoxide coating material obtained by the preparation method is uniform and is generally controlled to be between 2 and 3mm, so that the coating effect is better.
Preferably, the purity of the titanium powder in step (1) is 99.99% or more, such as 99.99%, 99.991%, 99.992%, 99.993%, 99.994%, 99.995% or 99.996%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the titanium dioxide powder has a purity of 99.99% or more, and may be, for example, 99.99%, 99.991%, 99.992%, 99.993%, 99.994%, 99.995% or 99.996%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mass ratio of the titanium dioxide powder to the titanium powder is (6.5-8.5):1, and may be, for example, 6.5:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1 or 8:1, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, in the first ball milling in the step (1), the mass ratio of the powder mixture to the milling balls is (5-10):1, and may be, for example, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the enumerated values, and other values not enumerated in the numerical range are also applicable.
In the present invention, the first ball milling process is performed while preventing oxidation of the powder, and a shielding gas is generally introduced, wherein the shielding gas comprises nitrogen and/or an inert gas, and is generally argon.
Preferably, the time of the first ball milling is not less than 24h, for example, 24h, 26h, 28h, 30h, 32h or 34h, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the pressure of the cold isostatic pressing in step (2) is 50 to 100MPa, for example 50MPa, 60MPa, 70MPa, 80MPa, 90MPa or 100MPa, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the burn-in treatment of step (3) includes evacuation, first burn-in, second burn-in and third burn-in which are sequentially performed.
In the invention, the pre-sintering treatment is preferably controlled to comprise vacuumizing, first pre-sintering, second pre-sintering and third pre-sintering in sequence, so that the density of the target material can be improved.
Preferably, the vacuum degree of the vacuum pumping in the step (3) is less than or equal to 1Pa, and may be, for example, 1Pa, 0.8Pa, 0.6Pa, 0.5Pa, 0.4Pa or 0.2Pa, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the temperature of the first pre-sintering is 1300-1450 ℃, such as 1300 ℃, 1320 ℃, 1340 ℃, 1360 ℃, 1380 ℃, 1400 ℃, 1420 ℃ or 1450 ℃, but not limited to the enumerated values, and other values not enumerated in the numerical range are also applicable.
In the present invention, the powder expands during the temperature rise, and the pressure is released after the pressure is increased to 10 MPa.
Preferably, the first pre-firing time is 0.5 to 1.5 hours, for example, 0.5 hour, 0.6 hour, 0.8 hour, 1 hour, 1.2 hour, 1.4 hour or 1.5 hours, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the second pre-baking is 1500-.
Preferably, the second pre-firing time is 0.5 to 1.5 hours, for example, 0.5 hour, 0.6 hour, 0.8 hour, 1 hour, 1.2 hour, 1.4 hour or 1.5 hours, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the third pre-sintering is 1680-.
Preferably, the time of the third pre-burning is 2-5h, for example, 2h, 3h, 4h or 5h, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, in the second ball milling in the step (3), the mass ratio of the pre-sintering material to the milling balls is (5-10):1, and for example, the pre-sintering material to the milling balls can be 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but the pre-sintering material and the milling balls are not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the time of the second ball milling is 10 to 24 hours, for example, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours or 24 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the time of the second ball milling is preferably controlled, so that the uniformity of the coating material can be improved.
Preferably, the sintering treatment in step (4) includes pressing, vacuum pumping, first sintering and second pressure sintering which are performed in sequence.
Preferably, the pressing pressure in step (4) is 0.05 to 0.1MPa, and may be, for example, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa or 0.1MPa, but is not limited to the values recited, and other values not recited in the range of values are also applicable.
Preferably, the pressing time is 3-10min, for example 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the vacuum degree of the vacuum pumping in the step (4) is less than 30Pa, such as 29Pa, 28Pa, 27Pa, 26Pa or 25Pa, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the temperature increase rate of the first sintering is 4-10 ℃/min, for example, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but is not limited to the values recited, and other values not recited within the range of values are also applicable.
Preferably, the end point temperature of the first sintering is 1350-.
Preferably, the holding time of the first sintering is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature increase rate of the second pressure sintering is 1-5 ℃/min, for example, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the second pressure sintering is performed while raising the temperature.
In the invention, the temperature rise in the second pressure sintering is preferably controlled and the pressure is applied at the same time, so that the density of the coating material can be further improved.
Preferably, the end point temperature of the second pressure sintering is 1600-.
Preferably, the final pressure of the second pressure sintering is 30 to 50MPa, for example, 30MPa, 35MPa, 40MPa, 45MPa or 50MPa, but the pressure is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, the final pressure of the second pressure sintering is preferably controlled, so that the density of the coating material can be further improved.
Preferably, the holding pressure time of the second pressure sintering is 3-8h, such as 3h, 4h, 5h, 6h, 7h or 8h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, after the heat preservation and pressure maintenance are finished, the heating is stopped, the temperature is reduced, the pressure is removed, the mold is taken out after the furnace is cooled to the temperature of less than 100 ℃, the mold is cooled to the room temperature, then the coating material is taken out of the mold, and the coating material is crushed and sieved to obtain the titanium pentoxide particles with uniform granularity.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing titanium powder and titanium dioxide powder according to the mass ratio of (6.5-8.5) to 1, and then carrying out first ball milling to obtain mixed powder, wherein the purity of the titanium powder is more than or equal to 99.99%, the purity of the titanium dioxide powder is more than or equal to 99.99%, the mass ratio of the mixed powder to grinding balls in the first ball milling is (5-10) to 1, and the time of the first ball milling is more than or equal to 24 hours;
(2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) under 50-100MPa to obtain a pressed blank;
(3) vacuumizing the pressed compact obtained in the step (2) until the final vacuum degree is less than or equal to 1Pa, sequentially performing first pre-sintering at 1300-;
(4) and (3) pressing the pre-sintered material obtained in the step (3) for 3-10min under 0.05-0.1MPa, then vacuumizing until the end vacuum degree is less than 30Pa, heating to 1350-.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention can effectively improve the density of the titanium pentoxide coating material, control the particle size of the titanium pentoxide and improve the uniformity of the titanium pentoxide, thereby improving the coating performance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a titanium pentoxide coating material, which comprises the following steps:
(1) mixing titanium powder and titanium dioxide powder according to the mass ratio of 7.5:1, and then carrying out first ball milling to obtain mixed powder, wherein the purity of the titanium powder is 99.99%, the purity of the titanium dioxide powder is 99.99%, the mass ratio of the mixed powder to grinding balls in the first ball milling is 7.5:1, and the first ball milling time is 24 hours;
(2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) under 75MPa to obtain a pressed blank;
(3) vacuumizing the green compact obtained in the step (2) until the final vacuum degree is 1Pa, sequentially performing first presintering for 1h at 1375 ℃, performing second presintering for 1h at 1550 ℃, performing third presintering for 3.5h at 1730 ℃, and performing second ball milling for 17h to obtain a presintering material, wherein in the second ball milling, the mass ratio of the presintering material to grinding balls is 7.5: 1;
(4) and (3) pressing the pre-sintered material obtained in the step (3) for 6.5min under 0.07MPa, then vacuumizing until the end vacuum degree is 29Pa, heating to 1400 ℃ at 7 ℃/min for carrying out first sintering for 2h, heating at 3 ℃/min, pressurizing while heating until the end temperature is 1690 ℃, and the end pressure is 40MPa, carrying out second pressure sintering, and carrying out heat preservation and pressure maintenance for 5.5h to obtain the trititanium pentoxide coating material.
Example 2
The embodiment provides a preparation method of a titanium pentoxide coating material, which comprises the following steps:
(1) mixing titanium powder and titanium dioxide powder according to the mass ratio of 6.5:1, and then carrying out first ball milling to obtain mixed powder, wherein the purity of the titanium powder is 99.991%, the purity of the titanium dioxide powder is 99.991%, the mass ratio of the mixed powder to grinding balls in the first ball milling is 10:1, and the time of the first ball milling is 25 hours;
(2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) under 50MPa to obtain a pressed blank;
(3) vacuumizing the pressed blank obtained in the step (2) until the final vacuum degree is 0.8Pa, sequentially performing first pre-sintering at 1450 ℃ for 0.5h, performing second pre-sintering at 1600 ℃ for 0.5h, performing third pre-sintering at 1680 ℃ for 5h, and performing second ball milling for 10h to obtain a pre-sintered material, wherein in the second ball milling, the mass ratio of the pre-sintered material to the grinding balls is 10: 1;
(4) and (3) pressing the pre-sintered material obtained in the step (3) for 10min under 0.05MPa, then vacuumizing until the end vacuum degree is 28Pa, heating to 1450 ℃ at 4 ℃/min for carrying out first sintering for 1h, heating at 5 ℃/min, pressurizing while heating until the end temperature is 1600 ℃, and keeping the end pressure at 50MPa, carrying out second pressure sintering, and keeping the temperature and the pressure for 3h to obtain the trititanium pentoxide coating material.
Example 3
The embodiment provides a preparation method of a titanium pentoxide coating material, which comprises the following steps:
(1) mixing titanium powder and titanium dioxide powder according to the mass ratio of 8.5:1, and then carrying out first ball milling to obtain mixed powder, wherein the purity of the titanium powder is 99.992%, the purity of the titanium dioxide powder is 99.992%, in the first ball milling, the mass ratio of the mixed powder to grinding balls is 5:1, and the first ball milling time is 26 hours;
(2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) under 100MPa to obtain a pressed blank;
(3) vacuumizing the pressed blank obtained in the step (2) until the final vacuum degree is 0.7Pa, sequentially performing first pre-sintering for 1.5h at 1300 ℃, performing second pre-sintering for 1.5h at 1500 ℃, performing third pre-sintering for 2h at 1780 ℃, and performing second ball milling for 24h to obtain a pre-sintered material, wherein in the second ball milling, the mass ratio of the pre-sintered material to the grinding balls is 5: 1;
(4) and (3) pressing the pre-sintered material obtained in the step (3) for 3min under 0.1MPa, then vacuumizing until the end point vacuum degree is 27Pa, heating to 1350 ℃ at the speed of 10 ℃/min for carrying out first sintering for 3h, heating at the speed of 1 ℃/min, simultaneously pressurizing when heating, and carrying out second pressure sintering and heat preservation and pressure preservation for 8h until the end point temperature is 1780 ℃ and the end point pressure is 30MPa, thus obtaining the trititanium pentoxide coating material.
Example 4
This example provides a method for preparing a titanium pentoxide coating material, which is different from that of example 1 only in that the first pre-firing is not performed, that is, step (3) is replaced with:
and (3) vacuumizing the pressed blank obtained in the step (2) until the final vacuum degree is 1Pa, sequentially performing second pre-sintering at 1550 ℃ for 1h, performing third pre-sintering at 1730 ℃ for 3.5h, and performing second ball milling for 17h to obtain a pre-sintered material, wherein in the second ball milling, the mass ratio of the pre-sintered material to the grinding balls is 7.5: 1.
Example 5
This example provides a method for preparing a titanium pentoxide coating material, which is different from that of example 1 only in that the second pre-firing is not performed, that is, step (3) is replaced with:
and (3) vacuumizing the pressed blank obtained in the step (2) until the final vacuum degree is 1Pa, sequentially performing first pre-sintering for 1h at 1375 ℃, performing third pre-sintering for 3.5h at 1730 ℃, and performing second ball milling for 17h to obtain a pre-sintered material, wherein in the second ball milling, the mass ratio of the pre-sintered material to the grinding balls is 7.5: 1.
Example 6
This example provides a method for preparing a titanium pentoxide coating material, which is different from that of example 1 only in that the third pre-firing is not performed, that is, step (3) is replaced by:
and (3) vacuumizing the pressed blank obtained in the step (2) until the final vacuum degree is 1Pa, sequentially performing first presintering for 1h at 1375 ℃, performing second presintering for 1h at 1550 ℃, and performing second ball milling for 17h to obtain a presintering material, wherein in the second ball milling, the mass ratio of the presintering material to the grinding balls is 7.5: 1.
Example 7
This example provides a method for preparing a titanium pentoxide coating material, which is different from that of example 1 only in that the time of the second ball milling is 5 h.
Example 8
This example provides a method for preparing a titanium pentoxide coating material, which is different from that of example 1 only in that the time of the second ball milling is 40 h.
Example 9
This example provides a method for preparing a titanium pentoxide coating material, which is different from example 1 only in that no pressurization is performed in the second pressure sintering, that is, step (4) is replaced with:
and (3) pressing the pre-sintered material obtained in the step (3) for 6.5min under 0.07MPa, then vacuumizing until the end vacuum degree is 29Pa, heating to 1400 ℃ at the speed of 7 ℃/min for carrying out first sintering for 2h, heating to 1690 ℃ at the end temperature at the speed of 3 ℃/min, and carrying out heat preservation for 5.5h to obtain the trititanium pentoxide coating material.
Example 10
This example provides a method for preparing a titanium pentoxide coating material, which is different from that of example 1 only in that the final pressure in the second pressure sintering is 20 MPa.
Example 11
This example provides a method for preparing a titanium pentoxide coating material, which is different from that of example 1 only in that the final pressure in the second pressure sintering is 70 MPa.
Comparative example 1
The comparative example provides a preparation method of a titanium pentoxide coating material, which is different from the preparation method of example 1 only in that the step (3) is removed, namely, the green compact obtained in the step (2) is directly sintered to obtain the titanium pentoxide coating material.
The density of the trititanium pentoxide coating materials prepared in examples 1 to 11 and comparative example 1 was measured by the drainage method, and the results are shown in table 1, where the density is measured as measured density/theoretical density × 100%.
The uniformity of the titanium pentoxide coating materials prepared in examples 1-11 and comparative example 1 was determined by: the obtained trititanium pentoxide coating material was sieved, and the uniformity was 2 to 3mm as the mass of the trititanium pentoxide coating material divided by the total mass of the trititanium pentoxide coating material, and the results are shown in table 1.
TABLE 1
| Density/%) | Degree of uniformity/%) | |
| Example 1 | 99 | 89 |
| Example 2 | 97 | 88 |
| Example 3 | 98 | 86 |
| Example 4 | 95 | 84 |
| Example 5 | 93 | 82 |
| Example 6 | 94 | 83 |
| Example 7 | 95 | 80 |
| Example 8 | 97 | 83 |
| Example 9 | 89 | 80 |
| Example 10 | 90 | 81 |
| Example 11 | 98 | 85 |
| Comparative example 1 | 85 | 40 |
From table 1, the following points can be seen:
(1) as can be seen from the data of examples 1 to 11, the preparation method provided by the invention can improve the compactness of the titanium pentoxide coating material to more than 89%, and improve the uniformity of the titanium pentoxide coating material to more than 80%.
(2) Comparing the data of the example 1 and the data of the examples 4 to 6, it can be seen that the differences between the examples 4 to 6 and the example 1 are only that the first pre-sintering, the second pre-sintering and the third pre-sintering are not performed respectively, and the compactness and the uniformity in the examples 4 to 6 are lower than those in the example 1, thereby showing that the first pre-sintering, the second pre-sintering and the third pre-sintering are preferably performed in sequence, and the compactness and the uniformity of the titanium pentoxide coating material can be improved.
(3) Comparing the data of example 1 and examples 7-8, it can be seen that the second ball milling time in example 1 is 17h, and the compactness and uniformity in examples 7-8 are lower than those in example 1 compared with the second ball milling time in examples 7-8 of 5h and 40h, respectively, which shows that the invention preferably controls the second ball milling time to improve the compactness and uniformity of the titanium pentoxide coating material.
(4) Comparing the data of example 1 and examples 9-11 together, it can be seen that the final pressure of the second pressure sintering in example 1 is 40MPa, the second pressure sintering in example 9 is not pressurized, the final pressures of the second pressure sintering in examples 10-11 are 20MPa and 70MPa respectively, and the compactness and uniformity of examples 9-11 are lower than those of example 1, thus showing that the invention prefers to pressurize in the second pressure sintering and control the final pressure of the pressurizing, and can improve the compactness and uniformity of the titanium pentoxide coating material.
(5) Comparing the data of example 1 and comparative example 1, it can be seen that the comparative example 1 is different from example 1 only in that step (3) is removed, and the compactness and uniformity in comparative example 1 are lower than those in example 1, thereby showing that the pre-sintering treatment and the second ball milling are preferably carried out in the invention, and the compactness and uniformity of the titanium pentoxide coating material can be improved.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the titanium pentoxide coating material is characterized by comprising the following steps of:
(1) mixing titanium powder and titanium dioxide powder, and performing first ball milling to obtain mixed powder;
(2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) to obtain a pressed blank;
(3) sequentially pre-sintering and carrying out second ball milling on the green compacts obtained in the step (2) to obtain pre-sintered materials;
(4) and (4) sintering the pre-sintered material obtained in the step (3) to obtain the titanium pentoxide coating material.
2. The preparation method according to claim 1, wherein the purity of the titanium powder in the step (1) is more than or equal to 99.99%;
preferably, the purity of the titanium dioxide powder is more than or equal to 99.99 percent;
preferably, the mass ratio of the titanium dioxide powder to the titanium powder is (6.5-8.5): 1.
3. The preparation method according to claim 1 or 2, characterized in that, in the first ball milling in the step (1), the mass ratio of the powder mixture to the grinding balls is (5-10): 1;
preferably, the time of the first ball milling is more than or equal to 24 h.
4. The production method according to any one of claims 1 to 3, wherein the pressure of the cold isostatic pressing treatment in step (2) is 50 to 100 MPa.
5. The manufacturing method according to any one of claims 1 to 4, wherein the pre-firing treatment of step (3) includes evacuation, first pre-firing, second pre-firing, and third pre-firing, which are sequentially performed.
6. The method according to claim 5, wherein the final vacuum degree of the evacuation in the step (3) is less than or equal to 1 Pa;
preferably, the temperature of the first pre-sintering is 1300-1450 ℃;
preferably, the time of the first pre-burning is 0.5-1.5 h;
preferably, the temperature of the second pre-sintering is 1500-1600 ℃;
preferably, the time of the second pre-burning is 0.5-1.5 h;
preferably, the temperature of the third pre-burning is 1680-;
preferably, the time of the third pre-burning is 2-5 h.
7. The preparation method according to any one of claims 1 to 6, wherein in the second ball milling in the step (3), the mass ratio of the pre-sintered material to the grinding balls is (5-10): 1;
preferably, the time of the second ball milling is 10 to 24 hours.
8. The production method according to any one of claims 1 to 7, wherein the sintering treatment in step (4) comprises pressing, vacuum evacuation, first sintering and second pressure sintering which are performed in this order.
9. The method according to claim 8, wherein the pressure of the pressing in the step (4) is 0.05 to 0.1 MPa;
preferably, the pressing time is 3-10 min;
preferably, the vacuum degree of the vacuumizing end in the step (4) is less than 30 Pa;
preferably, the temperature rise rate of the first sintering is 4-10 ℃/min;
preferably, the end temperature of the first sintering is 1350-;
preferably, the holding time of the first sintering is 1-3 h;
preferably, the heating rate of the second pressure sintering is 1-5 ℃/min;
preferably, the second pressure sintering is performed while raising the temperature;
preferably, the end temperature of the second pressure sintering is 1600-1780 ℃;
preferably, the final pressure of the second pressure sintering is 30-50 MPa;
preferably, the holding and pressure maintaining time of the second pressure sintering is 3-8 h.
10. The method of any one of claims 1 to 9, comprising the steps of:
(1) mixing titanium powder and titanium dioxide powder according to the mass ratio of (6.5-8.5) to 1, and then carrying out first ball milling to obtain mixed powder, wherein the purity of the titanium powder is more than or equal to 99.99%, the purity of the titanium dioxide powder is more than or equal to 99.99%, the mass ratio of the mixed powder to grinding balls in the first ball milling is (5-10) to 1, and the time of the first ball milling is more than or equal to 24 hours;
(2) carrying out cold isostatic pressing treatment on the mixed powder obtained in the step (1) under 50-100MPa to obtain a pressed blank;
(3) vacuumizing the pressed compact obtained in the step (2) until the final vacuum degree is less than or equal to 1Pa, sequentially performing first pre-sintering at 1300-;
(4) and (3) pressing the pre-sintered material obtained in the step (3) for 3-10min under 0.05-0.1MPa, then vacuumizing until the end vacuum degree is less than 30Pa, heating to 1350-.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111636052A (en) * | 2019-03-01 | 2020-09-08 | 宁波江丰电子材料股份有限公司 | Preparation method of target material |
| CN112225565A (en) * | 2020-10-14 | 2021-01-15 | 宁波江丰电子材料股份有限公司 | Preparation method of tungsten-silicon target blank |
| CN113213915A (en) * | 2021-04-15 | 2021-08-06 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of low-temperature trititanium pentoxide crystal coating material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636052A (en) * | 2019-03-01 | 2020-09-08 | 宁波江丰电子材料股份有限公司 | Preparation method of target material |
| CN112225565A (en) * | 2020-10-14 | 2021-01-15 | 宁波江丰电子材料股份有限公司 | Preparation method of tungsten-silicon target blank |
| CN113213915A (en) * | 2021-04-15 | 2021-08-06 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of low-temperature trititanium pentoxide crystal coating material |
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