CN108247035B - Graphene oxide/zirconium modified aluminum-based shape memory alloy particle for three-dimensional printing and preparation method thereof - Google Patents
Graphene oxide/zirconium modified aluminum-based shape memory alloy particle for three-dimensional printing and preparation method thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 91
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000010146 3D printing Methods 0.000 title claims abstract description 50
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 49
- -1 zirconium modified aluminum Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002923 metal particle Substances 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 150000003754 zirconium Chemical class 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- KFSUNTUMPUWCMW-UHFFFAOYSA-N ethanol;perchloric acid Chemical compound CCO.OCl(=O)(=O)=O KFSUNTUMPUWCMW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 19
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 239000006262 metallic foam Substances 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 239000004753 textile Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012781 shape memory material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 229910000683 memory titanium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920000431 shape-memory polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 230000000638 stimulation Effects 0.000 description 1
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Classifications
-
- B22F1/0003—
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y70/00—Materials specially adapted for additive manufacturing
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing and a preparation method thereof, wherein the aluminum-based shape memory alloy particles comprise modified zirconium metal particles and foam metal powder, and the preparation method comprises the following steps: treating the surface of the zirconium-containing metal particles by using a perchloric acid ethanol solution to remove an oxide layer and impurities on the surface, so as to obtain pretreated zirconium-containing metal particles; placing the pretreated zirconium-containing metal particles in a hydrogen absorption device, heating to remove hydrogen, and then placing the zirconium-containing metal particles in a hydrogen atmosphere for hydrogenation treatment to obtain surface-hydrogenated zirconium particles; soaking the zirconium particles subjected to surface hydrogenation treatment in a graphene oxide aqueous solution, mixing uniformly, taking out, drying and grinding to obtain graphene oxide modified zirconium particles; adding the graphene oxide modified zirconium particles into foamed aluminum powder and foamed nickel powder, heating in vacuum, stirring, mixing, grinding and sieving to obtain the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing.
Description
Technical Field
The invention belongs to the technical field of textile materials, and particularly relates to graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing and a preparation method thereof.
Background
The rapid prototyping technology is a part prototype manufacturing technology integrating the technical fields of technology, laser processing, CAD/CAM technology, numerical control technology, new materials and the like, divides three-dimensional model data designed by a computer into layer model data, and manufactures a physical model by adopting a method of piling up materials point by point or layer by layer on specific raw materials, and belongs to a discrete/piled-up forming method, namely layered entity manufacturing. The three-dimensional rapid forming technology is to spray liquid microdroplets or continuous molten material beams by using a nozzle, stack and form the microdroplets or continuous molten material beams layer by layer according to a certain path, and selectively spray an adhesive on a layer of paved powder material by using a spray head under the control of a computer according to the information of a section profile so as to bond partial powder and form a section layer. And after one layer is finished, the workbench descends one layer thick, powder is spread, the adhesive is sprayed, the subsequent layer is bonded, and the three-dimensional product is formed in a circulating mode.
The shape memory material is divided into a shape memory polymer, a shape memory alloy and a shape memory ceramic, is an intelligent material of which the shaped polymer can return to a pre-deformation state under the stimulation of external factors (such as heat, light, electricity, magnetism, pH and the like), and has wide application prospect in the fields of aerospace materials, novel medical equipment, intelligent biological materials, textiles, sports goods and the like. Chinese patent CN 104801704B discloses a shape memory alloy material for three-dimensional printing and a preparation method thereof, which comprises metal foam powder, shape memory alloy particles, alcohol-soluble resin and dispersing agent, wherein metal foam copper/aluminum/iron/nickel/magnesium/titanium/zinc powder is taken as a carrier, the shape memory titanium nickel/nickel manganese/titanium platinum alloy is fixed in the pores of the metal foam powder, dry powdery fine particles are prepared by the action of thermoplastic alcohol-soluble resin and the dispersing agent, and then the dry powdery fine particles are ground and sieved by a disc to obtain the three-dimensional printing shape memory alloy material, the shape of the product formed by the shape memory alloy material prepared by the method in three-dimensional printing is not influenced by the deformation of the shape memory alloy particles, so that the shape memory alloy with high compactness is obtained, and the shape memory alloy material contains the alcohol-soluble resin with thermoplastic property, the material has thermoplastic adhesiveness during three-dimensional printing. The high-toughness nanofiber reinforced rubber-based 3D printing material and the preparation method disclosed by the Chinese patent CN104761761B are obtained by mixing mixed rubber, a thermoplastic polymer nanofiber reinforced material and a solvent, and then shearing and blending the mixed rubber by a high-speed shearing machine, wherein the mixed rubber comprises raw rubber, tackifying resin, a reinforcing agent, a filler, a plasticizer, an anti-aging agent, an active agent, an accelerator and a vulcanizing machine, and the 3D printing material prepared by the method has the characteristics of high bonding strength and good toughness. It can be known from the prior art that the mechanical properties of the shape memory material can be significantly improved by adding the nano reinforcing material into the three-dimensional printing material.
Disclosure of Invention
The technical problem to be solved by the invention is to provide graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing and a preparation method thereof. The graphene oxide/zirconium oxide modified aluminum-based shape memory alloy particles for three-dimensional printing have the advantages of good surface stability, no high-temperature change, no crack, high strength, good freedom and flexibility of the preparation process, and capability of meeting the requirements of three-dimensional printing.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the graphene oxide/zirconium modified aluminum-based shape memory alloy particle for three-dimensional printing comprises a modified zirconium metal particle and foamed metal powder, wherein the modified zirconium metal particle is a graphene oxide modified zirconium particle, and the foamed metal powder is foamed aluminum powder and foamed nickel powder.
Preferably, in the above aspect, the graphene oxide-modified zirconium particles are obtained by attaching graphene oxide to surface-hydrotreated zirconium particles.
The invention also provides a preparation method of the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing, which is characterized by comprising the following steps of: the method comprises the following steps:
(1) treating the surface of the zirconium-containing metal particles by using a perchloric acid ethanol solution to remove an oxide layer and impurities on the surface, so as to obtain pretreated zirconium-containing metal particles;
(2) placing the pretreated zirconium-containing metal particles prepared in the step (1) in a hydrogen absorption device, heating to remove hydrogen, and then placing the metal particles in a hydrogen atmosphere for hydrogenation treatment to obtain surface-hydrogenated zirconium particles;
(3) dipping the surface-hydrotreated zirconium particles prepared in the step (2) into a graphene oxide aqueous solution, mixing uniformly, taking out, drying and grinding to obtain graphene oxide modified zirconium particles;
(4) and (4) adding the graphene oxide modified zirconium particles prepared in the step (3) into foamed aluminum powder and foamed nickel powder, heating in vacuum, stirring and mixing, and grinding and sieving to obtain the graphene oxide/zirconium oxide modified aluminum-based shape memory alloy particles for three-dimensional printing.
Preferably, in the step (1), the content of zirconium in the zirconium-containing metal particles is 80 to 95 wt%.
Preferably, in the step (1), the content of perchloric acid in the perchloric acid ethanol solution is 50 to 70 wt%.
Preferably, in the step (1), the treatment temperature is 50-60 ℃ and the treatment time is 45-60 min.
Preferably, in the step (2), the temperature for heating and dehydrogenation is 500-600 ℃, the time is 60-90min, and the vacuum degree is 2-5 Pa.
In the above aspect, the hydrogen absorption amount of the surface-hydrotreated zirconium particles in the step (2) is preferably 95%.
Preferably, in the step (3), the solid-to-solid ratio of the surface-hydrotreated zirconium particles to the graphene oxide aqueous solution is 1g:20-30 mL.
Preferably, in the step (4), the content of the foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 50-60 wt%, and the mass ratio of the foamed aluminum powder to the foamed nickel powder is 1: 0.3-0.4.
Compared with the prior art, the invention has the following beneficial effects:
(1) the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing prepared by the invention comprise graphene oxide modified zirconium particles, foamed aluminum powder and foamed nickel powder, the surfaces of the zirconium-containing metal particles are cleaned, the oxide layer and impurities on the surfaces are taken out, the surfaces of the zirconium-containing metal particles are cleaned, then the adsorbed substances, such as moisture and impurity gases, on the surfaces of samples are taken out by heating at high temperature, hydrogen is absorbed in the hydrogen atmosphere, the surfaces of the zirconium-containing metal particles are activated, the adhesion of the subsequent graphene oxide is more facilitated, the graphene oxide is partially reduced into graphene under the action of hydrogen when the foamed metal powder is subjected to vacuum heating treatment, the stability of the particles under heat and pressure in the three-dimensional printing process is further improved, the prepared product has great flexibility and free running, high designability and no crack trace, the strength is high, the fabric can meet the use requirements of multiple fields, the mechanical strength of the fabric of the textile can be obviously improved, and a good foundation is laid for preparing high-strength intelligent textiles.
(2) The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing can be used as a reinforcement and introduced into a composite material, the shape memory alloy particles are specific to the excitation reaction of heat and stress, high intelligence and versatility are obtained, a compact thin film can be formed on the surface of a textile through a three-dimensional printing technology, the thin film is good in flexibility, free of influence of external force, free of crack marks, uniform in thickness and high in strength, high-strength intelligent textiles can be prepared, and the method is suitable for the field of special protection.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1:
(1) and (2) soaking the metal particles containing 80 wt% of zirconium in 50 wt% of perchloric acid ethanol solution, treating for 45min at 50 ℃, and removing an oxide layer and impurities on the surface to obtain the pretreated metal particles containing zirconium.
(2) Placing the pretreated zirconium-containing metal particles in a hydrogen absorption device, vacuumizing to the vacuum degree of 2Pa, heating at 500 ℃ for 60min to remove hydrogen, and then placing in a hydrogen atmosphere for hydrogenation treatment for 30min to obtain surface-hydrogenated zirconium particles with the hydrogen absorption of 95%.
(3) According to the solid-to-material ratio of 1g:20mL, soaking the zirconium particles subjected to surface hydrogenation treatment in a graphene oxide aqueous solution of 5mg/L, mixing and uniformly mixing, taking out, drying at 90 ℃, and grinding to obtain the graphene oxide modified zirconium particles.
(4) Adding foamed aluminum powder and foamed nickel powder with the mass ratio of 1:0.3 into the graphene oxide modified zirconium particles, heating for 15min under vacuum degree of 0.5Pa and at 200 ℃, stirring, mixing, grinding and sieving to obtain the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing, wherein the content of foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 50 wt%.
Example 2:
(1) and (2) soaking the metal particles containing 95 wt% of zirconium in 70 wt% of perchloric acid ethanol solution, treating for 60min at 60 ℃, and removing an oxide layer and impurities on the surface to obtain the pretreated metal particles containing zirconium.
(2) Placing the pretreated zirconium-containing metal particles in a hydrogen absorption device, vacuumizing to the vacuum degree of 5Pa, heating at 600 ℃ for 90min to remove hydrogen, and then placing in a hydrogen atmosphere for hydrogenation treatment for 60min to obtain surface-hydrogenated zirconium particles with the hydrogen absorption of 95%.
(3) According to the solid-to-material ratio of 1g:30mL, soaking the zirconium particles subjected to surface hydrogenation treatment in a graphene oxide aqueous solution of 20mg/L, mixing and uniformly mixing, taking out, drying at 100 ℃, and grinding to obtain the graphene oxide modified zirconium particles.
(4) Adding foamed aluminum powder and foamed nickel powder with the mass ratio of 1:0.4 into the graphene oxide modified zirconium particles, heating for 30min under vacuum degree of 1Pa and at 250 ℃, stirring, mixing, grinding and sieving to obtain the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing, wherein the content of foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 60 wt%.
Example 3:
(1) and (2) soaking the metal particles containing 85 wt% of zirconium in an ethanol solution of 60 wt% perchloric acid, treating for 50min at 55 ℃, and removing an oxide layer and impurities on the surface to obtain the pretreated metal particles containing zirconium.
(2) Placing the pretreated zirconium-containing metal particles in a hydrogen absorption device, vacuumizing to the vacuum degree of 3Pa, heating at 550 ℃ for 75min to remove hydrogen, and then placing in a hydrogen atmosphere for hydrogenation treatment for 45min to obtain surface-hydrogenated zirconium particles with the hydrogen absorption of 95%.
(3) According to the solid-to-material ratio of 1g:25mL, soaking the zirconium particles subjected to surface hydrogenation treatment in a graphene oxide aqueous solution of 10mg/L, mixing and uniformly mixing, taking out, drying at 95 ℃, and grinding to obtain the graphene oxide modified zirconium particles.
(4) Adding foamed aluminum powder and foamed nickel powder with the mass ratio of 1:0.35 into the graphene oxide modified zirconium particles, heating for 20min under vacuum degree of 0.8Pa and at 230 ℃, stirring, mixing, grinding and sieving to obtain the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing, wherein the content of foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 55 wt%.
Example 4:
(1) and (2) soaking the metal particles containing 90 wt% of zirconium in 65 wt% of perchloric acid ethanol solution, treating for 55min at 53 ℃, and removing an oxide layer and impurities on the surface to obtain the pretreated metal particles containing zirconium.
(2) Placing the pretreated zirconium-containing metal particles in a hydrogen absorption device, vacuumizing to the vacuum degree of 4.5Pa, heating at 580 ℃ for 80min to remove hydrogen, and then placing in a hydrogen atmosphere for hydrogenation treatment for 40min to obtain surface-hydrogenated zirconium particles with the hydrogen absorption of 95%.
(3) According to the solid-to-material ratio of 1g:23mL, soaking the zirconium particles subjected to surface hydrogenation treatment in a graphene oxide aqueous solution of 15mg/L, mixing and uniformly mixing, taking out, drying at 95 ℃, and grinding to obtain the graphene oxide modified zirconium particles.
(4) Adding foamed aluminum powder and foamed nickel powder with the mass ratio of 1:0.34 into the graphene oxide modified zirconium particles, heating for 25min under vacuum degree of 0.8Pa and at 225 ℃, stirring, mixing, grinding and sieving to obtain the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing, wherein the content of foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 53 wt%.
Example 5:
(1) and (2) soaking the metal particles containing 80 wt% of zirconium in an ethanol solution of 70 wt% perchloric acid, treating for 60min at 50 ℃, and removing an oxide layer and impurities on the surface to obtain the pretreated metal particles containing zirconium.
(2) Placing the pretreated zirconium-containing metal particles in a hydrogen absorption device, vacuumizing to the vacuum degree of 2Pa, heating at 600 ℃ for 60min to remove hydrogen, and then placing in a hydrogen atmosphere for hydrogenation treatment for 60min to obtain surface-hydrogenated zirconium particles with the hydrogen absorption of 95%.
(3) According to the solid-to-material ratio of 1g:20mL, soaking the zirconium particles subjected to surface hydrogenation treatment in a graphene oxide aqueous solution of 20mg/L, mixing and uniformly mixing, taking out, drying at 90 ℃, and grinding to obtain the graphene oxide modified zirconium particles.
(4) Adding foamed aluminum powder and foamed nickel powder with the mass ratio of 1:0.4 into the graphene oxide modified zirconium particles, heating for 15min under vacuum degree of 0.5Pa and at 250 ℃, stirring, mixing, grinding and sieving to obtain the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing, wherein the content of foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 60 wt%.
Example 6:
(1) and (2) soaking the metal particles containing 95 wt% of zirconium in 50 wt% of perchloric acid ethanol solution, treating for 45min at 60 ℃, and removing an oxide layer and impurities on the surface to obtain the pretreated metal particles containing zirconium.
(2) Placing the pretreated zirconium-containing metal particles in a hydrogen absorption device, vacuumizing to the vacuum degree of 5Pa, heating at 500 ℃ for 90min to remove hydrogen, and then placing in a hydrogen atmosphere for hydrogenation treatment for 30min to obtain surface-hydrogenated zirconium particles with the hydrogen absorption of 95%.
(3) According to the solid-to-material ratio of 1g:30mL, soaking the zirconium particles subjected to surface hydrogenation treatment in a graphene oxide aqueous solution of 5mg/L, mixing and uniformly mixing, taking out, drying at 100 ℃, and grinding to obtain the graphene oxide modified zirconium particles.
(4) Adding foamed aluminum powder and foamed nickel powder with the mass ratio of 1:0.3 into the graphene oxide modified zirconium particles, heating for 30min under vacuum degree of 1Pa and at 200 ℃, stirring, mixing, grinding and sieving to obtain the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing, wherein the content of foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 50 wt%.
Through detection, the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing prepared in examples 1 to 6 are prepared on the surface of a cotton textile by using a three-dimensional printing technology to obtain a film material with the thickness of 1 μm, and the results of the appearance and the mechanical properties of the film material are as follows:
the above table shows that the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing can form a smooth crack-free micron-sized film on the surface of a textile, and endow the textile with shape memory performance on the basis of remarkably improving the mechanical strength of the textile.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A graphene oxide/zirconium modified aluminum-based shape memory alloy particle for three-dimensional printing, characterized in that: the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing comprise modified zirconium metal particles and foamed metal powder, wherein the modified zirconium metal particles are graphene oxide modified zirconium particles, and the foamed metal powder is foamed aluminum powder and foamed nickel powder;
the preparation method comprises the following steps:
(1) treating the surface of the zirconium-containing metal particles by using a perchloric acid ethanol solution to remove an oxide layer and impurities on the surface, so as to obtain pretreated zirconium-containing metal particles;
(2) placing the pretreated zirconium-containing metal particles prepared in the step (1) in a hydrogen absorption device, heating to remove hydrogen, and then placing the metal particles in a hydrogen atmosphere for hydrogenation treatment to obtain surface-hydrogenated zirconium particles;
(3) soaking the surface-hydrotreated zirconium particles prepared in the step (2) in a graphene oxide aqueous solution, mixing uniformly, taking out, drying and grinding to obtain graphene oxide modified zirconium particles;
(4) and (4) adding the graphene oxide modified zirconium particles prepared in the step (3) into foamed aluminum powder and foamed nickel powder, heating in vacuum, stirring and mixing, and grinding and sieving to obtain the graphene oxide/zirconium oxide modified aluminum-based shape memory alloy particles for three-dimensional printing.
2. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: the graphene oxide-modified zirconium particles are obtained by attaching graphene oxide to surface-hydrotreated zirconium particles.
3. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: in the step (1), the content of zirconium in the zirconium-containing metal particles is 80 to 95 wt%.
4. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: in the step (1), the content of perchloric acid in the perchloric acid ethanol solution is 50-70 wt%.
5. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: in the step (1), the treatment temperature is 50-60 ℃ and the treatment time is 45-60 min.
6. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: in the step (2), the temperature for heating and dehydrogenation is 500-600 ℃, the time is 60-90min, and the vacuum degree is 2-5 Pa.
7. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: in the step (2), the hydrogen absorption amount of the surface-hydrotreated zirconium particles was 95%.
8. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: in the step (3), the solid-to-material ratio of the surface-hydrotreated zirconium particles to the graphene oxide aqueous solution is 1g:20-30 mL.
9. The graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing according to claim 1, wherein: in the step (4), the content of the foamed metal powder in the graphene oxide/zirconium modified aluminum-based shape memory alloy particles for three-dimensional printing is 50-60 wt%, and the mass ratio of the foamed aluminum powder to the foamed nickel powder is 1: 0.3-0.4.
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