An alloy and a method of making the same

Abstract

The application discloses an alloy and a preparation method thereof, and the preparation method comprises the following steps: coating treatment is conducted on alloy powder by using a coating agent, so that the viscosity of the alloy powder is 0.5-3 Pa.s, and coated alloy powder is obtained; the coated alloy powder is mixed with photosensitive resin, a photoinitiator and a dispersing agent, and then ball milling treatment is conducted, so that alloy slurry is obtained; and the alloy is obtained by conducting ultraviolet light curing printing treatment on the alloy slurry. The preparation method of the alloy has the following advantages: 1. energy saving and environmental protection: the 3D printing is conducted in the ultraviolet light curing mode, compared with the traditional laser sintering or electron beam melting mode, high temperature is not needed, the energy consumption is greatly reduced, and the influence on the environment is also reduced; 2. simple operation: the 3D printing process of the application can be conducted in air, a vacuum or a protective gas environment is not needed, the operation is more simple, and it is beneficial to large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of advanced manufacturing technology, in particular to an alloy and a preparation method thereof. BACKGROUND

[0002] Titanium alloy has the advantages of small density, high strength, good corrosion resistance, stable high-temperature performance, good mechanical properties and fatigue resistance, and is widely used in aerospace and biomedical fields. Additive manufacturing, i.e. 3D printing technology, converts digital models into physical models through layer-by-layer stacking. Among them, the 3D printing technology of titanium alloy has attracted great attention due to its wide application in the fields of aerospace, biomedicine, mechanical manufacturing, etc.

[0003] At present, the main additive manufacturing method of titanium alloy is to melt or deposit titanium alloy powder into a target shape by laser beam, electron beam, electric arc, etc. as a heat source, and then stack layer by layer. The existing process methods of additive manufacturing of titanium alloy mainly include selective laser melting (SLM), selective laser sintering (SLS), electron beam selective melting (EBSM), wire-arc additive manufacturing (WAAM), etc. However, the above process methods have limitations. For example: for selective laser melting (SLM) and selective laser sintering (SLS) using laser as heat source, the raw material titanium alloy powder needs to be prepared by gas atomization method and strictly sieved, and at the same time, there are problems such as high energy consumption of laser power, difficult to control printing precision, low forming efficiency, high thermal stress of finished product, etc. in the printing process. For electron beam selective melting (EBSM) and wire-arc additive manufacturing (WAAM) using electron beam or electric arc as heat source, the substrate temperature needs to be strictly preheated and the atmosphere needs to be controlled during printing, which is more complicated to operate. The finished product prepared by additive manufacturing process of titanium alloy melting forming inevitably has defects such as dendritic growth, thermal cracks, pores, etc., and the equipment cost is high, which is difficult to carry out large-scale industrial production.

[0004] Therefore, the prior art still needs to be improved and developed. SUMMARY

[0005] In view of the above shortcomings of the prior art, the present application provides an alloy and a preparation method thereof, so as to solve the problems of high energy consumption and high equipment cost of the existing metal 3D printing technology.

[0006] The technical scheme adopted by the present application to solve the above technical problems is as follows:

[0007] In a first aspect of the present application, a preparation method of an alloy is provided, which comprises the following steps:

[0008] The alloy powder is coated with a coating agent to coat the alloy powder, so that the viscosity of the alloy powder is 0.5-3 Pa.s, and the coated alloy powder is obtained;

[0009] The coated alloy powder is mixed with a photosensitive resin, a photoinitiator and a dispersant, and then subjected to ball milling to obtain an alloy slurry;

[0010] The alloy slurry is subjected to ultraviolet curing printing to obtain the alloy.

[0011] Preferably, the alloy powder is a titanium alloy powder, an aluminum alloy powder, a copper alloy powder or a stainless steel powder.

[0012] Preferably, the coating agent is selected from one or more of styrene, acrylic acid, vinyl triethoxysilane and methyl methacrylate.

[0013] Preferably, the step of coating the alloy powder with the coating agent comprises:

[0014] The alloy powder and the silane coupling agent are dissolved in ethanol and stirred, and then the azobisisobutyronitrile and the coating agent are added in sequence under stirring to complete the coating of the alloy powder.

[0015] Preferably, the mass ratio of the alloy powder, the silane coupling agent and the coating agent is (1:1:2)-(1:1:5).

[0016] Preferably, the photosensitive resin is selected from one or more of 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, acryloyl morpholine, trimethylolpropane triacrylate and ditrimethylolpropane acrylate.

[0017] The photoinitiator is selected from one or more of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2,4,6-trimethylbenzoyl-di(p-tolyl) phosphine oxide.

[0018] The dispersant is selected from one or more of oleic acid, BYK-190, BYK-191, BYK-192 and BYK 410 of BIK Chemicals.

[0019] Preferably, the mass ratio of the coated alloy powder and the photosensitive resin is (5:3)-(10:3).

[0020] Preferably, the step of subjecting the alloy slurry to ultraviolet curing printing comprises:

[0021] The alloy slurry is placed in the corresponding area of the light curing printer, and the printing parameters are set as follows: the intensity of the ultraviolet light is 10-100 mW / cm 2 , the exposure time is 10-30 s, and the layer thickness is 30-60 μm, and the alloy is printed.

[0022] Preferably, after the alloy slurry is subjected to the ultraviolet light curing printing process, the alloy body obtained after the ultraviolet light curing printing process is further subjected to a degreasing process to remove excess moisture and photosensitive resin on the surface of the alloy body.

[0023] In a second aspect, the present application provides an alloy prepared by the above method.

[0024] Advantages:

[0025] The present application discloses an alloy and a preparation method thereof. The preparation method of the alloy has the following advantages: 1. The alloy slurry of the present application comprises photosensitive resin and coated alloy powder, which can effectively avoid defects such as high porosity and uneven structure caused by the difficulty in accurately controlling the melting and solidification process of alloy powder in traditional methods. 2. Energy saving and environmental protection: The present application uses ultraviolet light curing method for 3D printing, which does not require high temperature compared with traditional 3D printing methods such as laser sintering or electron beam melting, greatly reducing energy consumption and environmental impact. 3. Simple operation: The 3D printing process of the present application can be carried out in air without vacuum or protective gas environment, which is more convenient for large-scale production. 4. High efficiency: The ultraviolet light curing method of the present application greatly improves the speed of model making, thereby improving the efficiency of metal 3D printing. 5. Wide application range: The method of the present application is not only suitable for titanium alloy materials, but also suitable for high-strength alloys such as aluminum alloy, copper alloy and stainless steel, thereby expanding the application range of metal 3D printing technology. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 A light-cured 3D printed titanium alloy sample prepared in Example 1 of the present application;

[0027] Figure 2 Roughness test results of the light-cured 3D printed titanium alloy prepared in Example 1 of the present application;

[0028] Figure 3 Uniformity test results of the light-cured 3D printed titanium alloy prepared in Example 1 of the present application: (a) is a scanning electron micrograph of the sintered titanium alloy; (b) is a grain size statistical graph of the sintered titanium alloy. DETAILED DESCRIPTION

[0029] The present application provides an alloy and a preparation method thereof. In order to make the purpose, technical scheme and effect of the present application more clear and explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0030] The present application provides a preparation method of an alloy, which comprises the following steps:

[0031] The alloy powder is coated by using a coating agent, so that the viscosity of the alloy powder is 0.5-3 Pa.s, and the coated alloy powder is obtained.

[0032] The coated alloy powder is mixed with photosensitive resin, photoinitiator and dispersant, and then is subjected to ball milling treatment, so that the alloy slurry is obtained.

[0033] The alloy slurry is subjected to ultraviolet curing printing treatment, so that the alloy is obtained.

[0034] The preparation method of the alloy provided by the embodiment of the present application has the following advantages: 1. The alloy slurry of the present application comprises photosensitive resin and coated alloy powder, which can effectively avoid defects such as high porosity and uneven structure caused by the difficulty in accurately controlling the melting and solidification process of the alloy powder in the traditional method. 2. Energy saving and environmental protection: The present application adopts ultraviolet curing method for 3D printing, which does not require high temperature compared with traditional 3D printing methods such as laser sintering or electron beam melting, greatly reducing energy consumption and environmental impact. 3. Simple operation: The 3D printing process of the present application can be carried out in air without the need for vacuum or protective gas environment, making the operation more simple and facilitating large-scale production. 4. High efficiency: The ultraviolet curing method of the present application greatly improves the speed of model making, thereby improving the efficiency of metal 3D printing. 5. Wide application range: The method of the present application is not only suitable for titanium alloy materials, but also suitable for high-strength alloys such as aluminum alloy, copper alloy and stainless steel, thereby expanding the application range of metal 3D printing technology.

[0035] In some embodiments, the alloy powder is coated by using a coating agent, so that the viscosity of the alloy powder is 1 Pa.s, and the coated alloy powder is obtained.

[0036] In some embodiments, the alloy powder is titanium alloy powder, aluminum alloy powder, copper alloy powder or stainless steel powder.

[0037] The method of the embodiment of the present application is not only suitable for titanium alloy materials, but also suitable for high-strength alloys such as aluminum alloy, copper alloy and stainless steel, thereby expanding the application range of metal 3D printing technology.

[0038] In some embodiments, the coating agent is selected from one or more of styrene, acrylic acid, vinyl triethoxysilane and methyl methacrylate.

[0039] In some embodiments, the step of coating the alloy powder by using a coating agent is specifically as follows:

[0040] The alloy powder and silane coupling agent are dissolved in ethanol, stirred, and then azobisisobutyronitrile and coating agent are added in sequence under stirring to complete the coating treatment of the alloy powder.

[0041] The coating treatment of the alloy powder can reduce the agglomeration of the alloy powder and improve the solidification thickness. In the process of photocuring, the refractive index difference between the alloy powder without coating and the photosensitive resin is too large, which reduces the solidification thickness. After coating the surface of the alloy powder, the refractive index of the surface of the alloy powder is close to that of the resin, thereby improving the solidification thickness. Specifically, the alloy powder has hydroxyl groups, which react with the silane coupling agent, and then azobisisobutyronitrile as an initiator and a coating agent are introduced, thereby obtaining the coated alloy powder. The ethanol as the environmental liquid does not participate in the reaction, but can uniformly disperse the alloy powder and the silane coupling agent, so that they react more uniformly.

[0042] In some embodiments, the mass ratio of the alloy powder, the silane coupling agent and the coating agent is (1:1:2)-(1:1:5).

[0043] If the proportion of the silane coupling agent and the coating agent is too small, the surface of the alloy powder cannot be uniformly coated, and if it is too large, it will cause waste.

[0044] In some preferred embodiments, the mass ratio of the alloy powder, the silane coupling agent and the coating agent is 1:1:3.

[0045] In some embodiments, the photosensitive resin is selected from one or more of 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, acryloyl morpholine, trimethylolpropane triacrylate, and bistrimethylolpropane acrylate.

[0046] The photoinitiator is selected from one or more of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 2,4,6-trimethylbenzoyl-di (p-tolyl) phosphine oxide.

[0047] The dispersant is selected from one or more of oleic acid, BYK-190, BYK-191, BYK-192, and BYK 410 of BYK-Chemie.

[0048] In some embodiments, the mass ratio of the coated alloy powder and the photosensitive resin is (1:1:2)-(1:1:5).

[0049] In some preferred embodiments, the mass ratio of the coated alloy powder and the photosensitive resin is 10:3.

[0050] The ratio is the highest solid content that can be achieved at present, if the alloy powder ratio increases, the solidification thickness will decrease, resulting in printing failure; if the alloy powder ratio decreases, the shrinkage rate will increase in the sintering process, which is easy to bring greater shrinkage stress.

[0051] In some embodiments, the step of subjecting the alloy slurry to ultraviolet light solidification printing treatment specifically comprises:

[0052] Placing the alloy slurry in the corresponding area of the light solidification printer, setting the printing parameters: the intensity of ultraviolet light is 50 mW / cm², the exposure time is 10 s, and the layer thickness is 30 μm, and printing the alloy.

[0053] In some embodiments, after the alloy slurry is subjected to ultraviolet light solidification printing treatment, the alloy blank obtained after the alloy slurry is subjected to ultraviolet light solidification printing treatment is further subjected to a degreasing treatment to remove excess moisture and photosensitive resin on the surface of the alloy blank.

[0054] In some embodiments, the metal blank after the degreasing treatment is further subjected to a sintering treatment.

[0055] After degreasing and sintering, a high-density alloy model is obtained, which can effectively avoid the defects caused by the difficulty in accurately controlling the melting and solidification process of alloy powder in traditional methods, such as high porosity, uneven organization, etc.

[0056] In some embodiments, a preparation method of an alloy is provided, which comprises the following steps:

[0057] The alloy powder and the silane coupling agent are dissolved in ethanol according to a mass ratio of 1:1, and then stirred, and then azobisisobutyronitrile and a coating agent are added in sequence under stirring to obtain coated alloy powder;

[0058] The coated alloy powder is mixed with photosensitive resin, photoinitiator and dispersant, and then subjected to ball milling treatment to obtain alloy slurry;

[0059] Placing the alloy slurry in the corresponding area of the light solidification printer, setting the printing parameters: the intensity of ultraviolet light is 50 mW / cm², the exposure time is 10 s, and the layer thickness is 30 μm, and printing, obtaining an alloy blank, and subjecting the alloy blank to a degreasing treatment to remove excess moisture and photosensitive resin on the surface of the alloy blank, obtaining the alloy.

[0060] In the second aspect of the present application, an alloy is provided, which is prepared by the above preparation method.

[0061] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, and are not all the embodiments. They are only used to explain the present application, but not limit the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work belong to the protection scope of the present application.

[0062] Embodiment 1

[0063] Step one: Ti6Al4V powder with D50=10 microns and silane coupling agent KH570 were added to a 300 mL ethanol solution in a ratio of 30 g:30 g, and the mixture was stirred under a magnetic stirrer at 100℃ for 3 h. Then it was centrifuged at 20000 r / min for 5 min, washed with ethanol and dried in a drying oven at 100℃ for 48 h. Then the treated titanium alloy powder (Ti6Al4V powder) was added to a butanone solution, ultrasonically dispersed and stirred in a magnetic stirrer at 70℃, then 240 mg of azobisisobutyronitrile (AIBN) was added as an initiator, 15 mL of styrene was added dropwise after 30 min, and the reaction was carried out at a rotation speed of 350 r / min for 3 h. Then it was centrifuged at 20000 r / min for 5 min, washed with ethanol and dried to obtain the coated Ti6Al4V powder.

[0064] Step two: The coated Ti6Al4V powder (D50=10 microns) was mixed with 1,6-hexanediol diacrylate and trimethylolpropane triacrylate in a volume ratio of 45:45:10, and finally 2wt.% of TPO photoinitiator and 2wt.% of oleic acid dispersant were added, ball milling for 12 h at a rotation speed of 400 r / min to obtain the alloy slurry.

[0065] Step three: The alloy slurry was placed in a 3D printer, and the printing parameters were set, including the intensity of ultraviolet light was 50 mW / cm², the exposure time was 10 s, and the layer thickness was 30 microns. The 3D printer was started to obtain the alloy embryo. The 3D printer would solidify the alloy slurry layer by layer through ultraviolet curing according to the set parameters, forming the required alloy model. In this process, the 3D printer would accurately control the melting and solidification process of the alloy powder to avoid defects in the alloy model.

[0066] Step 4: Place the alloy billet in a furnace for degreasing. The furnace atmosphere is argon. Increase the temperature to 200℃ at a rate of 2℃ / min, then to 300℃ at a rate of 1℃ / min, hold for 120 min, increase to 500℃ at a rate of 0.5℃ / min, hold for 300 min, then to 800℃ at a rate of 8℃ / min, hold for 30 min, and finally to 1300℃ at a rate of 8℃ / min, hold for 120 min. This completes the degreasing and sintering process, yielding a finely structured Ti6Al4V component. (See attached image). Figure 1 .

[0067] Roughness and uniformity tests were performed on the Ti6Al4V structural component prepared in Example 1. (See attached figures.) Figure 2 and Figure 3 ,Depend on Figure 2 It can be seen that the roughness of the Ti6Al4V structure prepared in Example 1 is 3.61 μm, which is an order of magnitude smaller than that of laser printing. Figure 3 As shown in (a) and (b), the Ti6Al4V structure has equiaxed grains with uniform size and an average grain size of 23.21 μm. Compared with the elongated grains produced by laser fabrication, equiaxed grains are beneficial for improving the mechanical properties of the material.

[0068] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A method of producing an alloy, characterized by, The preparation method comprises the following steps: The alloy powder is coated with a coating agent to make the viscosity of the alloy powder 0.5-3 Pa.s, and coated alloy powder is obtained; The coated alloy powder is mixed with photosensitive resin, photoinitiator and dispersant, and then ball-milled to obtain alloy slurry; The alloy slurry is subjected to ultraviolet curing printing treatment to obtain the alloy; The alloy powder is titanium alloy powder, aluminum alloy powder, copper alloy powder or stainless steel powder; The coating agent is selected from one or more of styrene, acrylic acid, vinyl triethoxysilane and methyl methacrylate; The step of coating the alloy powder with a coating agent is specifically: The alloy powder and silane coupling agent are dissolved in ethanol and stirred, and then azobisisobutyronitrile and coating agent are added in sequence under stirring to complete the coating treatment of the alloy powder; The mass ratio of the alloy powder, silane coupling agent and coating agent is (1:1:2)-(1:1:5); The photosensitive resin is selected from one or more of 1,6-hexanediol diacrylate, ethylene glycol dimethyl acrylate, acryloyl morpholine, trimethylolpropane triacrylate and bistrimethylolpropane acrylate; The photoinitiator is selected from one or more of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide and 2,4,6-trimethylbenzoyl-di(p-tolyl) phosphine oxide; The dispersant is selected from one or more of oleic acid, BYK-190, BYK-191, BYK-192 and BYK410; The mass ratio of the coated alloy powder to photosensitive resin is (5:3)-(10:3); The step of ultraviolet curing printing treatment of the alloy slurry specifically comprises: The alloy slurry is placed in a corresponding area of a photocuring printer, and printing parameters are set: the intensity of ultraviolet light is 10-100 mW / cm 2 , the exposure time is 10-30 s, and the layer thickness is 30-60 μm, and the alloy is printed. After the ultraviolet curing printing treatment of the alloy slurry, the alloy blank obtained after the ultraviolet curing printing treatment is further subjected to degreasing treatment to remove excess moisture and photosensitive resin on the surface of the alloy blank.

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