CN106041078B - A kind of chromatic metallic 3D printing wire rod and preparation method thereof - Google Patents
A kind of chromatic metallic 3D printing wire rod and preparation method thereof Download PDFInfo
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- CN106041078B CN106041078B CN201610549969.3A CN201610549969A CN106041078B CN 106041078 B CN106041078 B CN 106041078B CN 201610549969 A CN201610549969 A CN 201610549969A CN 106041078 B CN106041078 B CN 106041078B
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- wire rod
- printing wire
- melting
- chromatic metallic
- pigment
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- 238000010146 3D printing Methods 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 74
- 239000002184 metal Substances 0.000 claims abstract description 74
- 239000000049 pigment Substances 0.000 claims abstract description 60
- 239000011370 conductive nanoparticle Substances 0.000 claims abstract description 38
- 238000007639 printing Methods 0.000 claims abstract description 15
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- MPZNMEBSWMRGFG-UHFFFAOYSA-N bismuth indium Chemical compound [In].[Bi] MPZNMEBSWMRGFG-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 8
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 229910003460 diamond Inorganic materials 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 2
- 239000003086 colorant Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229910052956 cinnabar Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 210000001161 mammalian embryo Anatomy 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N Indigo Chemical group N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001005836 Euchloe ausonia Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000598860 Garcinia hanburyi Species 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940117709 gamboge Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- -1 lithopone Chemical compound 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052957 realgar Inorganic materials 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUTLDIXHQPSHHQ-UHFFFAOYSA-N tin(iv) sulfide Chemical compound [S-2].[S-2].[Sn+4] TUTLDIXHQPSHHQ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a kind of chromatic metallic 3D printing wire rod and preparation method thereof; it freezes to be molded after being mixed by low-melting-point metal, pigment and conductive nano particle; then the wire rod of specific mechanical intensity, shape of cross section and length dimension is made, various specific colors can also be presented while conductive and mechanical strength is realized.The present invention has the metallic print wire rod of electric conductivity and rich colors concurrently while offer first, the aesthetic property and experience sense of made termination function device can be obviously improved, both the 3D mechanical printing characteristics of wire rod ensure that, but also with the electric conductivity of metal, the direct manufacture of colorful conductive printout is also assures that simultaneously, new 3D printing category can be opened, application value is notable.
Description
Technical field
The invention belongs to 3D printing technique field, and in particular to a kind of chromatic metallic 3D printing wire rod and preparation method thereof.
Background technology
3D printing is also referred to as increasing material manufacturing, because it in rapid shaping and manufacture view possesses a series of unique advantages, already
As the core realm paid attention to extensively both at home and abroad.In all kinds of 3D printings, metallic print is especially acknowledged as crown therein.When
Before, in existing 3D printing technique commonly use material predominantly and nonconducting plastic wire, such as ABS, PLA, they are general
For making plastic pattern or part, but it is not used to manufacture conductive-type electronic device.And on the other hand, using traditional metal
Consumptive material, because of the too high such as thousands of degree of its fusing point, the special printing device relied on is typically more costly, it is difficult to is generalized to wide
Big domestic consumer aspect.Therefore, academia and industrial quarters are also continuously attempting to new way in recent years.One of those it is breakthrough enter
Exhibition is to introduce low-melting-point metal, to realize the room temperature printing speed of metalwork；Or wire rod is made in low-melting-point metal, then use
Common 3D printer prints specific object.
However, regrettably, the newest liquid metal own color for being used for making wire rod that makes progress is relatively simple, nothing
Method meets requirement of the user to color under various occasions.In 3D printing circle, based on such factor, it is rich that industrial quarters is proposed color
Rich 3D printing wire rod, but existing wire rod is mainly the nonmetallic wire rod made of plastics, polymer etc. so far, thus still
It cannot be directly used to need the printing of conductive object.At the same time, industry gradually proposes color liquid metal ink in the recent period
Concept (such as Chinese patent publication No. CN105220013A announce color liquid metal), but this ink is in liquid form
Embody, it is impossible to be used for 3D printer as plastic wire；That is, ink and the function that wire rod undertakes are entirely different,
Finally there is also essential distinction in the component of functional product, production method and application link；Even if moreover, by existing liquid
Metallic ink is made wire rod, and its mechanical strength can not often meet requirement of the existing 3D printer to mechanical strength.Generally speaking,
Chromatic metallic printing wire rod available for conventional 3D printer is not yet provided both at home and abroad so far.
Therefore, present invention firstly provides the technological concept of chromatic metallic 3D printing wire rod, its purpose is just being to provide tool
There is metal 3D printing wire rod of various colors and preparation method thereof, to the existing technology category for existing 3D printing of taking on a new look.
The content of the invention
(1) technical problems to be solved
The shortcomings that to overcome existing 3D printing consumptive material technology and the traditional 3D printing wire rod of change are not provided simultaneously with electric conductivity
With the present situation of color, the present invention provides a kind of chromatic metallic 3D printing wire rod, by loaded in low-melting-point metal per se with
The pigment of color and the conductive nano particle for possessing certain strength, then freeze shaping to obtain the metal 3D printing of expected color
Wire rod, mechanical strength and varying hardness, and various shape of cross sections and different length situation are can be made into, available for making color
Gorgeous 3D electric conductors or more purposes.Present invention also offers the preparation method of the chromatic metallic 3D printing wire rod.
(2) technical scheme
To achieve the above object, the present invention provides a kind of chromatic metallic 3D printing wire rod, its raw material include low-melting-point metal,
Pigment and conductive nano particle；
The low-melting-point metal should be non-fusible at room temperature, and to keep solid wire rod so as to be used for 3D printer, it is wrapped
Include indium bismuth alloy In66.3Bi33.7, bismuth tin alloy Bi58Sn42, bismuth-base alloy BiIn21Sn12Pb18One or more in；
The conductive nano particle includes one kind or several in nano level titanium, niobium, tantalum, tungsten, diamond, silicon nitride etc.
Kind；
Preferably, the conductive nano particle diameter is 1nm-900nm；More preferably 500nm-900nm.
Preferably, the conductive nano grain shape is bar-shaped, cone-shaped, spherical, thread, tubulose, shelly or polygonal,
To strengthen wire rod mechanical strength.
Preferably, the mass ratio of the low-melting-point metal and the conductive nano particle is 30-95: 1.
Indium bismuth alloy In of the present invention66.3Bi33.7The mass content for referring to In and Bi in the alloy is respectively 66.3% He
33.7%.Other alloy implications are similar.
The pigment includes the one or more in natural pigment, artificial synthesized pigment；
Preferably, the natural pigment include natural minerals pigment cinnabar, laterite, realgar, peacock green, powdered whiting,
One or more in wollastonite, blanc fixe, talcum powder, mica powder, kaolin；Or animal origin pigment alkermes, day
One or more in right pearl white；Or plant origin pigment gamboge, alizarin red, it is indigo-blue in one or more；
Preferably, the artificial synthesized pigment includes the one or more in titanium white, lithopone, lead chromate yellow, barba hispanica；It is or big
One or more in rouge and powder, even yellowish, phthalocyanine blue, quinacridone.
The pigment can be directly appended in the metal that is in a liquid state；Preferably, the low-melting-point metal with it is described
The mass ratio of pigment is 10-100: 1, it is possible thereby to obtain the liquid metal material of different colourities according to specific proportioning.
Preferably, the particle diameter of the pigment is 10nm-1000nm；More preferably 10nm-500nm.
The cross section of the chromatic metallic 3D printing wire rod is circular, square or sheet, equivalent redius 0.01-3cm.
The length of the chromatic metallic 3D printing wire rod is 1-30000cm.
It is exemplified below several specific chromatic metallic 3D printing wire rods.
A kind of chromatic metallic 3D printing wire rod, its raw material include low-melting-point metal indium bismuth alloy In66.3Bi33.7, pigment and
Conductive nano particle；The conductive nano particle includes the one or more in titanium, niobium, tantalum, tungsten, diamond, silicon nitride etc.；Institute
It is 500nm-900nm to state conductive nano particle diameter；The conductive nano grain shape be bar-shaped, cone-shaped, it is spherical, thread,
Tubulose, shelly or polygonal；The mass ratio of the low-melting-point metal and the conductive nano particle is 30-95: 1；The eutectic
The mass ratio of point metal and the pigment is 10-100: 1.
A kind of chromatic metallic 3D printing wire rod, its raw material include low-melting-point metal bismuth tin alloy Bi58Sn42, pigment and nanometer
Conductive particle；The conductive nano particle includes the one or more in titanium, niobium, tantalum, tungsten, diamond, silicon nitride etc.；It is described to receive
The a diameter of 500nm-900nm of rice conductive particle；The conductive nano grain shape be bar-shaped, cone-shaped, spherical, thread, tubulose,
Shelly or polygonal；The mass ratio of the low-melting-point metal and the conductive nano particle is 30-95: 1；The low-melting-point metal
Mass ratio with the pigment is 10-100: 1.
A kind of chromatic metallic 3D printing wire rod, its raw material include low-melting-point metal bismuth-base alloy BiIn21Sn12Pb18, pigment
With conductive nano particle；The conductive nano particle includes the one or more in titanium, niobium, tantalum, tungsten, diamond, silicon nitride etc.；
The conductive nano particle diameter is 500nm-900nm；The conductive nano grain shape is bar-shaped, cone-shaped, spherical, silk
Shape, tubulose, shelly or polygonal；The mass ratio of the low-melting-point metal and the conductive nano particle is 30-95: 1；It is described low
The mass ratio of melting point metals and the pigment is 10-100: 1.
The present invention also provides the preparation method of above-mentioned chromatic metallic 3D printing wire rod, comprises the following steps：
S1：Raw material, i.e. low-melting-point metal, pigment and conductive nano particle needed for choosing on demand；
S2：The low-melting-point metal is heated to liquid condition；Preferably, the heat treatment temperature is higher than or waited
In the fusing point of the low-melting-point metal；It is further preferred that the heat treatment temperature is higher than the fusing point of the low-melting-point metal
30-600℃。
S3：The pigment is added in the low-melting-point metal of liquid as required, stirred；Preferably, magnetic is used
Power agitator stirs 0.5-5h；The conductive nano particle is added by proportioning again, stirs, obtains color liquid metal mixed
Thing；Preferably, with magnetic stirrer 0.5-5h；
S4：Gained color liquid metal mixture is injected in mould after subzero treatment, is cooled and shaped, you can.
Step S4 specifically includes the assembling die conduit that gained color liquid metal mixture is injected to specific void size
In, after watching its filling completely, mould is placed in low temperature environment, freezes to liquid metal mixture cooling, throws off mould afterwards
Have top half, the wire rod for freezing shaping is stripped out from the conduit of mould the latter half, you can obtain the thick embryo of wire rod；It is excellent
Selection of land, conduit cross section can be prototype, square, sheet；Preferably, low temperature environment can be water cooling, the cooling sky of refrigeration machine offer
Gas.The thick embryo surface burr of the wire rod is removed, that is, obtains described chromatic metallic 3D printing wire rod；It is wound on particular support part
It is upper standby.
The present invention further study show that, by gained color liquid metal mixture progress subzero treatment can preferably change
It is apt to the intensity of the chromatic metallic 3D printing wire rod, intensity can lift more than 10-60%.
Specifically, the subzero treatment includes gained color liquid metal mixture being first warming up to 180-300 DEG C, keeps
30-90min, quickly cooled down in the environment of being then placed in -190 DEG C to -230 DEG C again.Preferably, gained color liquid metal is mixed
Compound is first warming up to 300 DEG C, keeps 60min, is quickly cooled down in the environment of being then placed in -190 DEG C again.
Further, multiple subzero treatment can be carried out, i.e., above-mentioned heating, cooling procedure is repeatedly circulated, therefore ensured that
The quality of final 3D printing wire rod.Experiment shows, through the subzero treatment can make 3D printing wire strength lifting 10-60% with
On.
Above-mentioned subzero treatment specific steps can be that gained color liquid metal mixture is warming up to required temperature, keep one
Fix time, then drop onto and be cooled in advance using liquid nitrogen in the stainless steel plate conduit of required temperature, at this moment color liquid metal
Quick freezing can occur.
It must be noted that although (Chinese patent publication No. CN105220013A) has pointed out colour in the research of early stage
The concept of liquid metal ink, but this liquid ink is carried using form, printing type, function and material component and the present invention
The chromatic metallic 3D printing wire rod of confession is completely different.First, existing color liquid metallic ink is with bottled liquid form body
It is existing, and 3D printing wire rod of the present invention is worked in a manner of stringy solids fine rule；Secondly, color liquid metallic ink is to spray
Mode realizes printing, and is to form destination object in the plane；And chromatic metallic wire rod of the present invention then passes through the tooth of 3D printing
Released on the mechanical mechanisms such as wheel or conveyer belt, then extrude and be stacked into objective component.So the two is in final functional product
Essential distinction be present in component, production method and application link.Even if existing color liquid metallic ink is made into wire rod, its
Mechanical strength also tends to that requirement of the existing 3D printer to mechanical strength can not be met.
Different from existing color liquid metallic ink, chromatic metallic 3D printing wire rod operating temperature, viscosity, conveying and
Printing type has essential distinction therewith.That is, common liquid metal is not suitable as 3D printing wire rod.
In the past, 3D printing wire rod was mainly plastics, and people seldom consider to go to strengthen its mechanical strength using nano particle,
And for low-melting-point metal, because itself being metal, people also just no longer consider further to add nano particle to change thing
Property, but tend not to meet that 3D printer uses after actually such low-melting-point metal solidification.
It is an unexpected discovery of the invention that some specific liquid metals can be used as 3D printing wire rod, and there is excellent performance.
By select specific liquid metal, the specific conductive nano particle of addition and can be significantly improved using subzero treatment technology and
The mechanical strength of 3D printing wire rod is lifted, meets 3D printing demand.Research shows, with the nano-particle added in target material
Refinement, number of grain boundaries increased considerably, and intensity, toughness and the superplasticity of target material can be all greatly improved, and be passed through
Regulating and controlling nano particle source and addition manner turns into the important channel of development of new material.
Particularly, it is better than the nano-particle material of low-melting-point metal from electric conductivity, has been obviously improved leading for terminal wire
Electrically.For example, adding the 5-90% nano-titanium of diameter 50, niobium, tantalum, tungsten particle into bismuth indium alloy, lift its mechanical strength
About 10-80%.In addition, adding the conductive nano particle of the shapes such as bar-shaped, cone-shaped, liquid metal can be made to produce different hinges
State, obtain preferably mechanical strength, function expected from realization.
The fusing point of some common liquid metals is listed below：
| Gallium, 29.28 DEG C | Ga75.5In24.5, 16 DEG C | Ga62.5In21.5Sn16, 11 DEG C |
| Bi49In21Pb18Sn12, 58 DEG C | In66.3Bi33.7, 72 DEG C | Bi52Pb30Sn18, 96 DEG C |
| Bi58Sn42, 138 DEG C | Bi35In48.6Sn15.9Zn0.4, 58.3 DEG C |
(3) beneficial effect
1st, the existing application concept and technology category of the existing 3D printing wire rod of the invention that taken on a new look, provides mosaic gold first
The material of this brand new conception of category printing wire rod, have the rich colors of metal satisfactory electrical conductivity and pigment concurrently；
2nd, 3D printing wire rod provided by the invention, it is bright-colored possessing compared with existing plastics or polymerization species wire rod
Outside color, electric conductivity greatly reinforces, available for the function element printing required to electrical conductivity and rich colors；
3rd, chromatic metallic printing wire rod both ensure that 3D mechanical printing characteristics, but also with the electric conductivity of metal, go back simultaneously
Demand of the people to color is met, application value is notable；
4th, chromatic metallic 3D printing wire rod can be directly applied to easily in the 3D printer of domestic portable, in room temperature
Under produce function element.
5th, the proposition of chromatic metallic printing wire rod is ideational innovation to traditional metal materials, 3D printing consumptive material, can be by
This amplifies out a large amount of whole new set of applications.
Brief description of the drawings
The mixture schematic diagram (figure a) that Fig. 1 embodiment of the present invention low-melting-point metal forms with pigment, conductive nano particle,
Figure b is partial enlarged drawing；
The mold sections schematic diagram of chromatic metallic 3D printing wire rod is prepared under Fig. 2 liquid of the embodiment of the present invention；
Chromatic metallic 3D printing wire rod schematic diagram prepared by Fig. 3 embodiment of the present invention；
The mixture schematic diagram (figure c) of the low-melting-point metal of Fig. 4 comparative examples 1 and pigment composition, figure d is partial enlarged drawing.
In figure：1-low-melting-point metal；2-granules of pigments；The mixture of 3-low-melting-point metal and pigment；4-low melting point
Metal and pigment, the mixture of conductive nano particle；5-conductive nano particle；61-prepare the mold of wire rod；62-prepare
The lower mould of wire rod；7-manufactured chromatic metallic 3D printing wire rod.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Embodiment 1
As shown in Figure 1-2, a kind of chromatic metallic 3D printing wire rod, its raw material include low-melting-point metal 1, pigment 2 and nanometer
Conductive particle 5；The low-melting-point metal is indium bismuth alloy In66.3Bi33.7；The pigment is cinnabar；The conductive nano
Grain is particle diameter 600nm nano-titanium；
The mass ratio of wherein described low-melting-point metal, pigment and conductive nano particle is 40: 4: 1.
The present embodiment also provides the preparation method of the chromatic metallic 3D printing wire rod, comprises the following steps：
S1：The low melting point indium bismuth alloy In is weighed by proportioning66.3Bi33.7, pigment cinnabar and conductive nano particle titanium；
Wherein, indium bismuth alloy In66.3Bi33.7Preparation method include press quality proportioning 66.3：33.7 put indium metal and bismuth
Mixed in 300 DEG C of vacuum high temperature furnace environment, cooling forms；
S2：By the indium bismuth alloy In66.3Bi33.7It is heated to 180-300 DEG C；
S3：The pigment cinnabar is made to a diameter of 600nm particle, the indium bismuth of above-mentioned liquid condition is added to by proportioning
Alloy In66.3Bi33.7In, then it is stirred with magnetic stirring apparatus, stir speed (S.S.) 500rpm, mixing time 5h；Again by matching somebody with somebody
Than adding the conductive nano particle, it is stirred, stir speed (S.S.) 500rpm, mixing time 5h, is obtained with magnetic stirring apparatus
Color liquid metal mixture 4；
S4：The color liquid metal mixture 4 is warming up to 300 DEG C, 60min is kept, is then injected into a fixed gap chi
(referring to Fig. 3) in the 0.8mm diameter circular aperture shape conduits that the very little length combined by mold 61 and lower mould 62 is 1 meter,
Conduit is cooled to -190 DEG C with liquid nitrogen in advance, fast in the environment of mould is inserted into -190 DEG C to -230 DEG C after watching its filling completely
Quickly cooling but, to color liquid metal mixture 4 cooling freeze, throw off upper mold portion afterwards, by freeze shaping wire rod from
It is stripped out in the conduit of mould the latter half, you can obtain the thick embryo of chromatic metallic wire rod；
S5：The thick embryo surface burr of chromatic metallic wire rod is removed, that is, the circle for obtaining length as 1 meter, a diameter of 0.8mm is color
Non-ferrous metal 3D printing wire rod 7 (referring to Fig. 3).It is wound on standby on particular support part.
The Radial Conductivity of gained chromatic metallic 3D printing wire rod is 6.3 × 106S/m, extrusion temperature are 192 DEG C, density
For 4.31g/cm3；Intensity meets the requirement of 3D printing wire rod.
Embodiment 2-11
Chromatic metallic 3D printing wire rod, its raw material includes low-melting-point metal, pigment and conductive nano particle, with embodiment 1
To differ only in pigment type different (granules of pigments diameter is identical).The preparation method of the chromatic metallic wire rod is the same as embodiment 1.
Embodiment 2-11 chromatic metallic 3D printing wire strengths are satisfied by the requirement of 3D printing wire rod.
Embodiment 12-20
Chromatic metallic 3D printing wire rod, its raw material include the conduction of low-melting-point metal 1, pigment 2 and a diameter of 300nm nanometers
Particle 5, from embodiment 1 to differ only in conductive nano particle type different (see the table below).The chromatic metallic 3D printing wire rod
Preparation method with embodiment 1.Embodiment 12-20 chromatic metallic 3D printing wire strengths are satisfied by the requirement of 3D printing wire rod.
Embodiment 21
Chromatic metallic 3D printing wire rod, its raw material includes low-melting-point metal 1, pigment 2 and conductive nano particle 5, with implementation
Example 1 differs only in low-melting-point metal difference, and the low-melting-point metal of chromatic metallic printing wire rod is bismuth tin alloy
Bi58Sn42。
The preparation method of the present embodiment chromatic metallic 3D printing wire rod differs only in step S2 differences with embodiment 1,
The present embodiment preparation method step S2 is included bismuth tin alloy Bi58Sn42Constant temperature 2 hours in 260 DEG C of vacuum constant-temperature container are placed in,
Then use magnetic stirrer 120 minutes, the bismuth tin alloy Bi of liquid is made58Sn42。
Wherein, bismuth tin alloy Bi58Sn42Preparation method include：Pure bismuth is weighed respectively according to the ratio of mass ratio 58: 42
And pure tin, it is put into rustless steel container, container is placed in constant temperature 1 hour in 230 DEG C of vacuum constant-temperature container, then uses magnetic agitation
Device stirs 100 minutes, that is, bismuth tin alloy Bi is made58Sn42, its fusing point is 138 DEG C.
The intensity of gained chromatic metallic 3D printing wire rod meets the requirement of 3D printing wire rod.
Embodiment 22
Chromatic metallic 3D printing wire rod, its raw material includes low-melting-point metal 1, pigment 2 and conductive nano particle 5, with implementation
Example 21 differs only in the nanometer niobium that the conductive nano particle is diameter 300nm；Wherein, wherein the low-melting-point metal 1,
The mass ratio of pigment 2 and the particle of conductive nano niobium 5 is 95: 4: 1.
The preparation method of the chromatic metallic 3D printing wire rod is the same as embodiment 1.
The intensity of gained chromatic metallic 3D printing wire rod meets the requirement of 3D printing wire rod.
Embodiment 23
Chromatic metallic 3D printing wire rod, its raw material includes low-melting-point metal 1, pigment 2 and conductive nano particle 5, with implementation
Example 1 differs only in low-melting-point metal difference, and the low-melting-point metal of the chromatic metallic wire rod is bismuth-base alloy
BiIn21Sn12Pb18。
The preparation method of the present embodiment chromatic metallic 3D printing wire rod differs only in step S2 differences with embodiment 1.
The present embodiment preparation method step S2 is included bismuth-base alloy BiIn21Sn12Pb18It is placed in constant temperature 4 in 250 DEG C of vacuum constant-temperature container
Hour, then with magnetic stirrer 50 minutes, the bismuth-base alloy BiIn of liquid is made21Sn12Pb18。
Wherein, bismuth-base alloy BiIn21Sn12Pb18Preparation method include：According to mass ratio 49:21:12:18 ratio point
Pure bismuth, pure indium, pure tin and pure lead also known as are taken, is put into rustless steel container, container is placed in constant temperature in 250 DEG C of vacuum constant-temperature container
4 hours, then use magnetic stirrer 50 minutes, that is, bismuth-base alloy BiIn is made21Sn12Pb18, its fusing point is 58 DEG C.
The Radial Conductivity of gained chromatic metallic 3D printing wire rod is 5.4 × 106S/m, extrusion temperature are 183 DEG C, density
For 5.23g/cm3, intensity meets the requirement of 3D printing wire rod.
Embodiment 24-35
Chromatic metallic 3D printing wire rod, its raw material includes low-melting-point metal, pigment and conductive nano particle, with embodiment 1-
11 differ only in pigment type difference.The pigment (a diameter of 600nm particle) is added to one by the present embodiment in advance
Liquid paint is made in a little solvents, is blended in again with liquid metal after cooling and shaping required chromatic metallic wire rod is made afterwards.
Solvent described here can be the material such as transparent silicon rubber, epoxy resin, PDMS (dimethyl silicone polymer) even through
Colored paint and coating toning form, and the mass ratio of the pigment and solvent is 1：10.
Embodiment 36
Chromatic metallic 3D printing wire rod, its raw material include low-melting-point metal, pigment and diameter 500nm nano-titanium particles, with
The differ only in low-melting-point metal and the mass ratio of pigment of embodiment 1 are 20: 1, the matter of melting point metals and nano-titanium particle
Amount ratio is 60: 1.
The chromatic metallic wire rod preparation method is same as Example 1.
The Radial Conductivity of gained chromatic metallic 3D printing wire rod is 6.2 × 106S/m, extrusion temperature are 176 DEG C, density
For 5.67g/cm3, intensity meets the requirement of 3D printing wire rod.
Embodiment 37
The present embodiment is based on existing chromatic metallic wire rod, and the liquid metal of required color is configured to by toning.Specifically will
2-6 classes chromatic metallic is made after liquid and mixed once again as made from above-described embodiment 1-25, the quality between different chromatic metallics
Than for 1-10 scopes, to mix colours into the metal wire rod of specific color.
Embodiment 38
The difference of the present embodiment and embodiment 1-37 is that wire cross-section is shaped as 0.8mm*0.8mm wire rod.
Embodiment 39
The difference of the present embodiment and embodiment 1-37 is that wire cross-section is shaped as the wire rod that the length of side is 1.5mm.
Embodiment 40
The difference of the present embodiment and embodiment 1-37 is, the environment for cooling down wire rod is cold using 5 DEG C of temperature
Water cools.
Comparative example 1
(wherein 3 represent the mixture of low-melting-point metals and pigment) as shown in Figure 4, original is differed only in embodiment 1
Material does not include conductive nano particulate gold.Find that it can not form wire rod or intensity difference after being prepared by the method for embodiment 1, can not pass through
Conventional 3D printer push.
Comparative example 2
With differing only in low-melting-point metal indium bismuth alloy In for embodiment 166.3Bi33.7Replace with gallium or gallium-indium alloy.
Find that it can not form wire rod or intensity difference after being prepared by the method for embodiment 1, main reason is that fusing point is low, during squeezing
It has been melted that, be not used to 3D conventional printers.
Comparative example 3
Do not include conductive nano particle with differing only in for embodiment 36.Find it not after being prepared by the method for embodiment 1
Wire rod or intensity difference can be formed, and skin-friction force is excessive, can not be pushed by conventional 3D printer.
Comparative example 4
Preparation method is differed only in embodiment 1 without subzero treatment, i.e., by S4 color liquids metal described in step
Mixture is directly injected into mould without heating treatment, is subsequently placed in -80 DEG C of environment and is cooled down.
It was found that it can not form wire rod or intensity difference, wire rod is excessively soft, and mechanical strength is relatively low, and skin-friction force is excessive, nothing
Method is pushed by conventional 3D printer.
Experimental example
The conductive characteristic method of testing of chromatic metallic 3D printing wire rod refers to the conventional method described in electrotechnics textbook
Carry out.The present invention can obtain indium bismuth alloy In from representative experimental data66.3Bi33.7Blend cinnabar pigment and conductive nano
The resistivity after wire rod is made with the situation of change of low-melting-point metal volume fraction in grain, and one of case is, if low melting point
When the mass ratio of metal and pigment is 20: 1 (comparative example 3), made chromatic metallic wire rod resistivity is 2.1 × 10- 6Ohmm, for the good conductor of electricity.On this basis, then in mass ratio 60: 1 load 500nm diameters nano-titaniums (embodiment 36),
The resistivity lifting about 6.6 × 10 of chromatic metallic wire rod prepared by hybrid technique can be obtained-7Ohmm, illustrate nanometer
The loading of particle so that electric conductivity be better than before chromatic metallic wire rod, also illustrate the present invention feasibility.Remaining, by more
The chromatic metallic wire rod prepared of different low-melting-point metal base components and pigment or even nano particle, also obtains similar component
Relation.It is numerous herein.
Embodiment above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row limits, on the premise of design spirit of the present invention is not departed from, technical side of this area ordinary skill technical staff to the present invention
The all variations and modifications that case is made, it all should fall into the protection domain of claims of the present invention determination.
Claims (16)
1. a kind of chromatic metallic 3D printing wire rod, it is characterised in that its raw material includes low-melting-point metal, pigment and conductive nano
Grain；The low-melting-point metal includes indium bismuth alloy In66.3Bi33.7, bismuth tin alloy Bi58Sn42, bismuth-base alloy BiIn21Sn12Pb18In
One or more；The conductive nano particle include nano level titanium, niobium, tantalum, tungsten, diamond, one kind in silicon nitride or
It is several；
The preparation method of the chromatic metallic 3D printing wire rod, comprises the following steps：
S1：Raw material needed for choosing on demand；
S2：The low-melting-point metal is heated to liquid condition；
S3：The pigment is added in the low-melting-point metal of liquid as required, stirred；Again as described in adding proportioning
Conductive nano particle, stirs, and obtains color liquid metal mixture；
S4：Gained color liquid metal mixture is injected in mould after subzero treatment, is cooled and shaped, you can；
The subzero treatment includes gained color liquid metal mixture being first warming up to 180-300 DEG C, keeps 30-90min, so
Quickly cooled down in the environment of being placed in -190 DEG C to -230 DEG C again afterwards.
2. chromatic metallic 3D printing wire rod according to claim 1, it is characterised in that the chromatic metallic 3D printing wire rod
Preparation method in, the subzero treatment includes gained color liquid metal mixture being first warming up to 300 DEG C, keeps 60min,
Then quickly cooled down in the environment of being placed in -190 DEG C again.
3. chromatic metallic 3D printing wire rod according to claim 1, it is characterised in that the chromatic metallic 3D printing wire rod
Preparation method in carry out multiple subzero treatment.
4. the chromatic metallic 3D printing wire rod according to claim any one of 1-3, it is characterised in that the conductive nano
Grain is shaped as bar-shaped, cone-shaped, spherical, thread, tubulose, shelly or polygonal.
5. the chromatic metallic 3D printing wire rod according to claim any one of 1-3, it is characterised in that the conductive nano
The a diameter of 1nm-900nm of grain；And/or the particle diameter of the pigment is 10nm-1000nm.
6. the chromatic metallic 3D printing wire rod according to claim any one of 1-3, it is characterised in that the conductive nano
Grain diameter 500nm-900nm；And/or the particle diameter of the pigment is 10nm-500nm.
7. the chromatic metallic 3D printing wire rod according to claim any one of 1-3, it is characterised in that the low-melting-point metal
Mass ratio with the conductive nano particle is 30-95: 1, and/or, the mass ratio of the low-melting-point metal and the pigment is
10-100∶1。
8. the chromatic metallic 3D printing wire rod according to claim any one of 1-3, it is characterised in that the pigment includes day
One or more in right pigment, artificial synthesized pigment.
9. the chromatic metallic 3D printing wire rod according to claim any one of 1-3, it is characterised in that the chromatic metallic 3D
The cross section of printing wire rod is circular, square or sheet, equivalent redius 0.01-3cm.
10. the preparation method of any one of the claim 1-9 chromatic metallic 3D printing wire rods, it is characterised in that including following
Step：
S1：Raw material needed for choosing on demand；
S2：The low-melting-point metal is heated to liquid condition；
S3：The pigment is added in the low-melting-point metal of liquid as required, stirred；Again as described in adding proportioning
Conductive nano particle, stirs, and obtains color liquid metal mixture；
S4：Gained color liquid metal mixture is injected in mould after subzero treatment, is cooled and shaped, you can.
11. preparation method according to claim 10, it is characterised in that the step 2) heat treatment temperature is higher than or waited
In the fusing point of the low-melting-point metal.
12. preparation method according to claim 11, it is characterised in that the step 2) heat treatment temperature is higher than described
30-600 DEG C of the fusing point of low-melting-point metal.
13. preparation method according to claim 10, it is characterised in that the stirring is magnetic agitation 0.5-5h.
14. according to the preparation method described in claim any one of 10-13, it is characterised in that the subzero treatment is included institute
Obtain color liquid metal mixture and be first warming up to 180-300 DEG C, keep 30-90min, be then placed in -190 DEG C to -230 DEG C again
Quickly cooled down under environment.
15. preparation method according to claim 14, it is characterised in that the subzero treatment is included gained color liquid
Metal mixture is first warming up to 300 DEG C, keeps 60min, is quickly cooled down in the environment of being then placed in -190 DEG C again.
16. preparation method according to claim 15, it is characterised in that carry out multiple subzero treatment.
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| CN201610549969.3A CN106041078B (en) | 2016-07-13 | 2016-07-13 | A kind of chromatic metallic 3D printing wire rod and preparation method thereof |
| PCT/CN2017/089409 WO2018010531A1 (en) | 2016-07-13 | 2017-06-21 | Colored metallic 3d-printing material and manufacturing method thereof |
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| CN106041078B (en) * | 2016-07-13 | 2017-11-21 | 北京梦之墨科技有限公司 | A kind of chromatic metallic 3D printing wire rod and preparation method thereof |
| CN106953075B (en) * | 2017-03-20 | 2018-01-12 | 国建新材料产业发展研究院（深圳）有限公司 | A kind of silicon liquid state metal composite lithium cell cathode material and preparation method |
| CN108044938B (en) * | 2017-12-12 | 2020-06-12 | 浙江蒂彩工艺品股份有限公司 | Synchronous printing method for filamentous materials for 3D printing |
| CN108342614B (en) * | 2018-05-17 | 2019-08-23 | 深圳市美信电子有限公司 | A kind of 3D printing metal material and 3D printing metal device |
| CN108746596B (en) * | 2018-06-29 | 2019-06-11 | 北京梦之墨科技有限公司 | A kind of 3D printing metal material and preparation method thereof and application method |
| CN109047768B (en) * | 2018-08-30 | 2021-07-13 | 云南科威液态金属谷研发有限公司 | Low-melting-point metal wire for 3D printing |
| CN109203320A (en) * | 2018-10-27 | 2019-01-15 | 泉州市联控自动化科技有限公司 | A kind of production method of the dedicated paraffin of 3D printer |
| CN110205517A (en) * | 2019-06-26 | 2019-09-06 | 广东省焊接技术研究所（广东省中乌研究院） | A method of refinement Sn-Bi system solder alloy eutectic structure |
| US11813656B2 (en) | 2019-09-25 | 2023-11-14 | Honda Motor Co., Ltd. | Low melting temperature metal fill for additively manufactured tools |
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