CN116121577A - Eutectic ceramic particle reinforced titanium-based composite material, preparation method thereof and 3D laser printing method - Google Patents

Eutectic ceramic particle reinforced titanium-based composite material, preparation method thereof and 3D laser printing method Download PDF

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CN116121577A
CN116121577A CN202310012630.XA CN202310012630A CN116121577A CN 116121577 A CN116121577 A CN 116121577A CN 202310012630 A CN202310012630 A CN 202310012630A CN 116121577 A CN116121577 A CN 116121577A
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powder
eutectic ceramic
reinforced titanium
particle reinforced
ceramic particle
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CN116121577B (en
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徐仰立
骆培辉
黄国钦
韩光耀
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Nan'an Huada Stone Industry Technology Research Institute
Huaqiao University
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Nan'an Huada Stone Industry Technology Research Institute
Huaqiao University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20Direct sintering or melting
    • B22F10/28Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • B33Y70/10Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Civil Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to the technical field of 3D printing materials, in particular to a eutectic ceramic particle reinforced titanium-based composite material, a preparation method thereof and a 3D laser printing method. The preparation method comprises the following steps: (1) To micron-sized Al 2 O 3 Powder and nanoscale ZrO 2 Powder mixing, wherein the Al 2 O 3 The powder accounts for 50wt% or more of the total amount of the mixed powder, and the balance is ZrO 2 A powder; (2) Soaking the mixed powder in alcohol, performing ball milling for 5-10min at 170-230rpm for 4-5h in an intermittent ball milling mode of stopping 5-10min each time, and drying to obtain eutectic ceramic powder; (3) Ball-milling and mixing the eutectic ceramic powder and the titanium alloy powder, and then drying and filtering by a screen to obtain the eutectic ceramic particle reinforced titanium-based composite material with the particle size of 20-45 mu m. The composite material prepared by the method improves the high-temperature hardness of Ti6Al4V formed by laser selective melting, and can be used for forming part products with high-temperature environments and complex shapes in service.

Description

Eutectic ceramic particle reinforced titanium-based composite material, preparation method thereof and 3D laser printing method
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to a eutectic ceramic particle reinforced titanium-based composite material, a preparation method thereof and a 3D laser printing method.
Background
The Ti6Al4V alloy is an important material for manufacturing high-performance parts and is widely applied to the fields of aerospace, marine equipment and the like. Along with the continuous development of industry, the requirements on the shape complexity and the high temperature resistance of Ti6Al4V parts are higher and higher, and the development of the process method of the complex Ti6Al4V parts with excellent high temperature performance has important significance.
By adding the ceramic component into the Ti6Al4V, the high-temperature performance of the Ti6Al4V material is improved. The adoption of the laser selective melting to form the ceramic particle reinforced titanium-based composite material is an effective way for manufacturing the complex Ti6Al4V component with excellent high-temperature performance. However, the addition of ceramic materials can lead to cracking of Ti6Al4V during additive manufacturing, ultimately leading to failure in forming.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a manufacturing method of a crystalline ceramic particle reinforced titanium matrix composite material.
Another object of the present invention is to provide a crystalline ceramic particle-reinforced titanium-based composite material produced by the aforementioned production method;
it is a further object of the present invention to provide a method of 3D laser printing of the aforementioned composite material.
One of the technical schemes provided by the invention is as follows:
a method for manufacturing a eutectic ceramic particle reinforced titanium matrix composite, comprising the steps of:
(1) To micron-sized Al 2 O 3 Powder and nanoscale ZrO 2 Powder mixing, wherein the Al 2 O 3 The powder accounts for 50wt% or more of the total amount of the mixed powder, and the balance is ZrO 2 A powder;
(2) Soaking the mixed powder in alcohol, performing ball milling for 5-10min at 170-230rpm for 4-5h in an intermittent ball milling mode of stopping 5-10min each time, and drying to obtain eutectic ceramic powder;
(3) Ball-milling and mixing the eutectic ceramic powder and the titanium alloy powder, and then drying and filtering by a screen to obtain the eutectic ceramic particle reinforced titanium-based composite material with the particle size of 20-45 mu m.
In a more preferred embodiment, the titanium alloy powder is Ti6Al4V.
In a more preferred embodiment, the Al 2 O 3 The particle size of the powder is 5-8 μm, and the ZrO 2 The particle size of the powder is 200-300nm.
In a more preferred embodiment, the Al 2 O 3 Powder and ZrO 2 The mass ratio of the powder is (50 wt% -60 wt%) (40 wt% -50 wt%).
In a more preferred embodiment, the eutectic ceramic powder is present in the eutectic ceramic reinforced titanium matrix composite in an amount of 3vol%.
In a more preferred embodiment, the ball milling is performed with a ball mill ball to mixed powder mass ratio of 4:1-6:1.
In a more preferred embodiment, the eutectic ceramic powder and titanium alloy powder are continuously ball milled for 24-25 hours at a revolution of 100-150 rpm.
In a more preferred embodiment, the drying temperature in step (2) is 75-85 ℃ and the drying time is more than 4 hours.
In a more preferred embodiment, the drying temperature in step (3) is 75-85 ℃ and the drying time is more than 4 hours.
The second technical scheme provided by the invention is as follows:
the eutectic ceramic particle reinforced titanium matrix composite material prepared by the manufacturing method.
The third technical scheme provided by the invention is as follows:
a 3D laser printing method, comprising: placing a printing material in a 3D printing working environment, adjusting the temperature of a substrate of a printer to 200 ℃, printing under the conditions that the laser power is 150-350W, the laser scanning speed is 600-1200 mm/s, the scanning interval is 0.1-0.12mm and the laser spot diameter is 50-80 mu m, and finishing printing on the substrate according to a preset printing program;
the printing material adopts the eutectic ceramic particle reinforced titanium matrix composite material.
The eutectic ceramic powder has a normal temperature hardness of 380-420MPa and a hardness of 280-300MPa at 800 ℃.
In summary, the present application includes at least one of the following beneficial technical effects:
the eutectic ceramic particle reinforced titanium-based composite material prepared by the method provided by the invention effectively improves the high-temperature hardness of Ti6Al4V formed by laser selective melting, and can be used for forming part products with complicated shapes in a high-temperature environment in service.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
For a clearer description of embodiments of the invention or of the solutions of the prior art, the drawings that are needed in the description of the embodiments or of the prior art will be briefly described, it being obvious that the drawings in the description below are some embodiments of the invention, and that other drawings can be obtained from them without inventive effort for a person skilled in the art; the positional relationships described in the drawings in the following description are based on the orientation of the elements shown in the drawings unless otherwise specified.
FIG. 1 is a flow chart of a eutectic ceramic reinforced titanium matrix composite material from fabrication to printing according to an embodiment of the present invention;
fig. 2 is an electron microscope image of eutectic ceramic composite powder provided by the invention: (a) an alumina powder electron microscope image (b) a zirconia powder electron microscope image (c) a Ti6Al4V powder electron microscope image (d) a eutectic ceramic powder electron microscope image (e) a eutectic ceramic reinforced titanium-based composite material electron microscope image;
FIG. 3 is a graph of hardness at various temperatures for a sample of 3% eutectic ceramic powder content and a sample of 0% eutectic ceramic powder content;
FIG. 4 is a graph showing measured hardness at various temperatures for a 0% eutectic ceramic powder content sample and a 3% eutectic ceramic powder content sample: (a) measured hardness map of 0% sample at 25 ℃ (b) measured hardness map of 0% sample at 200 ℃ (c) measured hardness map of 0% sample at 400 ℃ (d) measured hardness map of 0% sample at 600 ℃ (e) measured hardness map of 0% sample at 800 ℃ (f) measured hardness map of 3% sample at 25 ℃ (g) measured hardness map of 3% sample at 200 ℃ (h) measured hardness map of 3% sample at 400 ℃ (i) measured hardness map of 3% sample at 600 ℃ (j) measured hardness map of 3% sample at 800 ℃).
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
An embodiment of the invention provides a method for manufacturing a eutectic ceramic particle reinforced titanium matrix composite, which comprises the following steps:
(1) To micron-sized Al 2 O 3 Powder and nanoscale ZrO 2 Powder mixing, wherein the Al 2 O 3 The powder accounts for 50wt% or more of the total amount of the mixed powder, and the balance is ZrO 2 A powder; in the present embodiment, however, the micro-scale Al 2 O 3 The particle size of the powder was 6. Mu.m, the ZrO 2 The particle size of the powder is 220nm; the Al is 2 O 3 Powder and ZrO 2 The mass ratio of the powder is 57.5wt%:41.5wt%.
(2) After the mixed powder is soaked in alcohol, the intermittent ball milling mode of stopping for 5-10min at the speed of 170-230rpm for 5-10min is adopted, the duration is 4-5h, and in the embodiment, the mass ratio of the ball milling balls to the materials is 4:1, ball milling at 200rpm for 4h in an intermittent ball milling mode of 5min and 5min stop each time, and drying at 80 ℃ for 24h to obtain eutectic ceramic powder, wherein argon is adopted for protection in the drying process.
Notably, the micrometer-sized Al 2 O 3 The melting point of the powder was 2313K, and the present invention particularly uses micron-sized Al with a powder ratio of (50 wt% to 60 wt%) 2 O 3 Powder and nanoscale ZrO 2 Powder, preferably 57.5wt%:41.5wt% of eutectic particle powder capable of mixing micro-sized Al under the condition of the ratio 2 O 3 The melting point of the powder was reduced from 2313K to 2133K, allowing for micron-sized Al 2 O 3 The powder is better melted, and the two oxide eutectic ceramic powders in the ratio can effectively inhibitCracking caused by the manufacturing process. The ball milling speed of the mixed powder in a roller is 170-230rpm, preferably 200rpm, the mixed powder is ball milled for 4-5h in an intermittent ball milling mode of stopping for 5-10min, preferably 4h in an intermittent ball milling mode of stopping for 5min, the drying temperature of the powder after ball milling is 75-85 ℃, preferably 80 ℃ to enable the powder to be dried and agglomerated after all moisture, and then the powder is filtered by a 100-mesh screen after simple grinding treatment to obtain the composite powder.
(3) The eutectic ceramic powder and the titanium alloy powder were ball-milled and mixed, in this example, the titanium alloy powder was Ti6Al4V, the eutectic ceramic powder was 3vol%, and the titanium alloy powder was 97vol%, specifically, 194ml of Tl6Al4V and 6ml of Al were contained in 200ml 2 O 3 -ZrO 2 The mass of 194ml of Ti6Al4V is about 501.72g,6ml of Al 2 O 3 -ZrO 2 The inventors have found that, when the content of the eutectic ceramic powder is increased, the molding effect of the mixed composite material is deteriorated, and the performance of the composite material is affected, and when the content is decreased, the hardness is not effectively ensured due to the low content, as the mass is about 6.36g, which is an average approximate value obtained by filling the powder into the measuring cylinder 3 times. The eutectic ceramic powder and the titanium alloy powder are subjected to uninterrupted ball milling for 24 hours at the revolution of 120rpm, then are dried for 4 hours at the temperature of 75-85 ℃, are filtered by a screen, and the particle size of the powder of the composite material is detected by a particle size analyzer, and the result shows that the eutectic ceramic particle reinforced titanium-based composite material with the particle size distribution of 20-45 mu m is obtained;
the 3D laser printing method of the eutectic ceramic particle reinforced titanium-based composite material belongs to laser selective melting printing, namely sending the dried eutectic ceramic particle reinforced titanium-based composite material into an SLM printer for laser 3D printing, specifically, setting up 30 rectangular blocks with different input parameters and sizes of 10mm multiplied by 12mm in a 125mm multiplied by 125mm substrate for parameter inspection printing. For 30 samples, the layer thicknesses (H) of samples No. 1-30 are 30 μm, wherein the sample scanning interval (D) of samples No. 1-15 is 0.12mm, and the scanning interval (D) of samples No. 16-30 is 0.1mm; the laser power (P) is increased from 150W at 50W power up to 350W; the scanning speed (V) increases from 600mm/s up to 1200mm/s in 300 mm/s; the laser power and the scanning speed increment are synchronously carried out; the scanning interval is 0.12mm; the layer thickness is 30 μm; the laser spot diameter was 70 μm. The prepared 3vol% eutectic ceramic composite material powder is subjected to laser 3D printing by adopting the set parameters, and the mixed powder contains eutectic ceramic particles, so that the first layer is set to be printed twice for improving the stability of the sample on the substrate, and finally the sample with the best forming effect is selected.
After printing, the normal temperature hardness of the selected sample is measured by using an iVicky V2.0 Vickers hardness tester, and the result shows that the laser power is 300W, the scanning speed is 900mm/s and the scanning interval is 0.12mm; the layer thickness is 30 μm; under the condition that the laser spot diameter is 70 mu m, the composite material powder has the best effect after 3D printing, and can reach 403.62MPa when the eutectic ceramic particle content is 3vol% at normal temperature and only reaches 330.94MPa when the eutectic ceramic particle content is 0 vol%; the high temperature hardness of the sample at 800 ℃ is measured by using an HTV-PHS30 high temperature Vickers hardness tester, and the result shows that the eutectic ceramic content at the high temperature is 291.55MPa when the eutectic ceramic content is 3vol% and 220.59MPa when the eutectic ceramic content is 0 vol%.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention. In addition, unless otherwise specified, the starting materials employed may also be commercially available products conventionally used in the art or may be prepared by methods conventionally used in the art.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. A method for manufacturing a eutectic ceramic particle reinforced titanium matrix composite, comprising the steps of:
(1) To micron-sized Al 2 O 3 Powder and nanoscale ZrO 2 Powder mixing, wherein the Al 2 O 3 The powder accounts for 50wt% or more of the total amount of the mixed powder, and the balance is ZrO 2 A powder;
(2) Soaking the mixed powder in alcohol, performing ball milling for 5-10min at 170-230rpm for 4-5h in an intermittent ball milling mode of stopping 5-10min each time, and drying to obtain eutectic ceramic powder;
(3) Ball-milling and mixing the eutectic ceramic powder and the titanium alloy powder, and then drying and filtering by a screen to obtain the eutectic ceramic particle reinforced titanium-based composite material with the particle size of 20-45 mu m.
2. The method for producing a eutectic ceramic particle reinforced titanium matrix composite according to claim 1, wherein: the Al is 2 O 3 The particle size of the powder is 5-8 μm, and the ZrO 2 The particle size of the powder is 200-300nm.
3. The method for producing a eutectic ceramic particle reinforced titanium matrix composite according to claim 1, wherein: the Al is 2 O 3 Powder and ZrO 2 The mass ratio of the powder is (50 wt% -60 wt%) (40 wt% -50 wt%).
4. The method for producing a eutectic ceramic particle reinforced titanium matrix composite according to claim 1, wherein: in the eutectic ceramic reinforced titanium matrix composite, the content of the eutectic ceramic powder is 3vol%.
5. The method for producing a eutectic ceramic particle reinforced titanium matrix composite according to claim 1, wherein: the mass ratio of ball grinding balls to mixed powder used in the ball milling is 4:1-6:1.
6. The method for producing a eutectic ceramic particle reinforced titanium matrix composite according to claim 1, wherein: the eutectic ceramic powder and the titanium alloy powder are subjected to uninterrupted ball milling for 24-25 hours at the revolution of 100-150 rpm.
7. The method for producing a eutectic ceramic particle reinforced titanium matrix composite according to claim 1, wherein: the drying temperature in the step (2) is 75-85 ℃ and the drying time is more than 4 hours.
8. The method for producing a eutectic ceramic particle reinforced titanium matrix composite according to claim 1, wherein: the drying temperature in the step (3) is 75-85 ℃ and the drying time is more than 4 hours.
9. A eutectic ceramic particle reinforced titanium matrix composite made by the method of any one of claims 1-8.
10. A method of 3D laser printing, comprising: placing a printing material in a 3D printing working environment, adjusting the temperature of a substrate of a printer to 200 ℃, printing under the conditions that the laser power is 150-350W, the laser scanning speed is 600-1200 mm/s, the scanning interval is 0.1-0.12mm and the laser spot diameter is 50-80 mu m, and finishing printing on the substrate according to a preset printing program;
the printing material adopts the eutectic ceramic particle reinforced titanium-based composite material as claimed in claim 9.
CN202310012630.XA 2023-01-05 2023-01-05 Eutectic ceramic particle reinforced titanium-based composite material, preparation method thereof and 3D laser printing method Active CN116121577B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101063187A (en) * 2007-05-23 2007-10-31 济南钢铁股份有限公司 Preparation method of ceramic-metal composite material
CN103193486A (en) * 2013-03-18 2013-07-10 大连理工大学 Method for laser engineered net shaping of Al2O3-ZrO2 eutectic ceramic structure
KR20180029732A (en) * 2016-09-13 2018-03-21 한화테크윈 주식회사 Composite material products manufacturing method using the 3D printing process
CN108000004A (en) * 2017-12-11 2018-05-08 哈尔滨工业大学 A kind of preparation method of titanium flux-cored wire for 3D printing titanium matrix composite
WO2018100251A1 (en) * 2016-11-30 2018-06-07 Abdelmadjid Djemai Titanium-zirconium alloy and method for the production thereof by means of additive manufacturing
CN110037813A (en) * 2019-04-24 2019-07-23 广东省材料与加工研究所 A kind of titanium-based zirconium oxide composite material medical implant and its 3D printing preparation method
CN113215441A (en) * 2021-04-21 2021-08-06 上海材料研究所 SLM (Selective laser melting) -molding-based nanoparticle reinforced titanium-based composite material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101063187A (en) * 2007-05-23 2007-10-31 济南钢铁股份有限公司 Preparation method of ceramic-metal composite material
CN103193486A (en) * 2013-03-18 2013-07-10 大连理工大学 Method for laser engineered net shaping of Al2O3-ZrO2 eutectic ceramic structure
KR20180029732A (en) * 2016-09-13 2018-03-21 한화테크윈 주식회사 Composite material products manufacturing method using the 3D printing process
WO2018100251A1 (en) * 2016-11-30 2018-06-07 Abdelmadjid Djemai Titanium-zirconium alloy and method for the production thereof by means of additive manufacturing
CN108000004A (en) * 2017-12-11 2018-05-08 哈尔滨工业大学 A kind of preparation method of titanium flux-cored wire for 3D printing titanium matrix composite
CN110037813A (en) * 2019-04-24 2019-07-23 广东省材料与加工研究所 A kind of titanium-based zirconium oxide composite material medical implant and its 3D printing preparation method
CN113215441A (en) * 2021-04-21 2021-08-06 上海材料研究所 SLM (Selective laser melting) -molding-based nanoparticle reinforced titanium-based composite material and preparation method thereof

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