CN106378447A - Thermoelectric material powder suspension liquid for 3D printing and preparation method thereof - Google Patents
Thermoelectric material powder suspension liquid for 3D printing and preparation method thereof Download PDFInfo
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- CN106378447A CN106378447A CN201610125086.XA CN201610125086A CN106378447A CN 106378447 A CN106378447 A CN 106378447A CN 201610125086 A CN201610125086 A CN 201610125086A CN 106378447 A CN106378447 A CN 106378447A
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- 239000000463 material Substances 0.000 title claims abstract description 140
- 239000000843 powder Substances 0.000 title claims abstract description 140
- 239000000725 suspension Substances 0.000 title claims abstract description 63
- 238000010146 3D printing Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 title abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 29
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001238 wet grinding Methods 0.000 claims description 10
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 230000005619 thermoelectricity Effects 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 238000007641 inkjet printing Methods 0.000 abstract description 17
- 238000007639 printing Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 39
- 238000000227 grinding Methods 0.000 description 30
- 239000000758 substrate Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 14
- 229910005642 SnTe Inorganic materials 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000000280 densification Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- 229910018989 CoSb Inorganic materials 0.000 description 1
- 229910019739 Mg2Si1-xSnx Inorganic materials 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 241000921268 Selago corymbosa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
Classifications
-
- B22F1/0003—
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention provides a thermoelectric material powder suspension liquid for 3D printing. The thermoelectric material powder suspension liquid is characterized by comprising thermoelectric material powder, a dispersing agent and a solvent. The suspension liquid can be adopted as ink for 3D ink-jet printing and can be used for printing parts of a thermoelectric material device, wherein the viscosity of the ink can be regulated through regulating the content of solid and the content of an additive according to the specific requirement of nozzles required by different printing; the particle size of the thermoelectric powder can be controlled to be 45 [mu]m or below according to the difference of hole diameters of the nozzles; the solid content of the suspension liquid is 1 to 40% by volume percent; and relative to the powder, the dispersing agent is 5% to 50% by volume percent. According to the method, the preparation technology is simple, and the method has the prospect of scale production.
Description
Technical field
The present invention relates to a kind of thermoelectric material powder suspension for 3D printing and preparation method thereof, belong to thermoelectric material preparing technical field.
Background technology
Thermoelectric material is a kind of functional material being directly realized by directly conversion between electric energy and heat energy, and available Seebeck effect is converted into electric energy heat energy, realizes thermo-electric generation, is possible with paltie effect, electric energy is converted into heat energy, realize temperature-difference refrigerating.
The preparation of Conventional thermoelectric device is to be realized by way of subtracting material manufacture.First, material requested powder body is prepared by simple substance raw material, after powder body put in mould obtain thermoelectric material block by means such as sintering, then block cutting is become required form, then block is connected with electrode material.The device fabrication process of this complex process not only results in the waste of raw material, and cannot prepare the device with labyrinth and the microdevice with fine structure.
In recent years, the increases material manufacturing technology including ink-jet 3D printing is subject to the extensive attention of domestic and international researcher.Ink-jet 3D printing is to eject uniform drop by shower nozzle, and shower nozzle or substrate pass through dimensionally to move so that drop, by putting line, by line to face again to body, is accurately deposited on the printing quickly realizing three dimensional structure on substrate according to the route of design simultaneously.This manufacturing technology have the advantages that manufacture process no waste of material, the device that complicated shape can be prepared or there is fine structure, the preparation of several functions structure member can be carried out using multiple inks using multiple shower nozzles simultaneously.For thermo-electric device, print while achievable N-type and p-type bi-material, the device with labyrinth can be manufactured, also manufacture micro thermoelectric device.
The key of ink-jet 3D printing technique successful print thermo-electric device is the allotment of ink used by printing.Ink will have good stability, and the size of diameter of particle will be distributed in rational scope, and particle diameter easily makes greatly very much shower nozzle block, the too small densification being unfavorable for device of particle diameter.Solid phase particles size in the ink of existing inkjet printing is respectively less than 1 μm, is unfavorable for the later stage densification of thermoelectric material.Meanwhile, in order that the device printing has good thermoelectricity capability, the additive types adding in ink will be lacked as far as possible, and the amount of addition is low as far as possible, and the later stage easily removes it is easy to the densification of printed product.Ink droplet it is necessary first to overcome the absorption of shower nozzle capillary force, could smoothly spray in course of injection.Secondly, the formula of ink can directly affect the appearance of the wettability with substrate contact for the ink droplet and unnecessary satellite point in course of injection.Additionally, ink droplet after matrix deposition be subject to surface tension gradient effect so that in ink solute from center to surrounding directional migration, coffee toroidal effect occurs.The ink of function admirable can print the finished product of function admirable by adjusting Ma Langgeni flowing with effect of surface tension ink droplet on matrix for its viscosity thus controlling the effect of coffee ring.
Content of the invention
The technical problem to be solved is to provide a kind of thermoelectric material powder suspension for 3D printing and preparation method thereof for the deficiency of above-mentioned prior art presence, in suspension, the species of additive is few and content is low, later stage easily removes, and performance that thermoelectric material originally have has been effectively ensured.
The present invention by solving the problems, such as adopted technical scheme set forth above is：
A kind of thermoelectric material powder suspension for 3D printing, it includes thermoelectric material powder, dispersant, solvent.
By such scheme, the solid content that this is used for the thermoelectric material powder suspension of 3D printing can be between 1～40% with volume percentage, and wherein dispersant can be between 5%～50% with respect to thermoelectric material powder percent by volume.Solid content=the V of this suspension1/(V1+V2+V3), dispersant is relative to thermoelectric material powder volume content=V3/V1, wherein V1For thermoelectric material powder volume, it is calculated by powder quality and density of material, V2For solvent volume, V3For dispersant volume.
By such scheme, below 45 μm, wherein more than 1 μm of particle fraction can not be less than 90% to the granularity of described thermoelectric material powder, and more than 10 μm of particle fraction can not be less than 50%.
By such scheme, described dispersant is one of Polyvinylpyrrolidone (PVP), benzoic acid or PEG-4000 etc. or several mixture in any proportion.
By such scheme, described solvent is one of liquid such as water, dehydrated alcohol, acetone or several mixture in any proportion.
By such scheme, described thermoelectric material powder is p-type thermoelectric compound, can be selected from Bi2-xSbxTe3、SnSe、CeFe4Sb12、MnSi1.75、Cu2Se、Zr0.5Hf0.5Any one in CoSb and PbSe etc.；Described thermoelectric material powder is N-shaped thermoelectric compound, can be selected from Bi2Te3-xSex、SnTe、n-Co4Sb12-xTex、Mg2Si1-xSnx, any one in ZrNiSn and PbS etc..Technical scheme of the present invention is applied to arbitrary system thermoelectric material powder, and here only illustrates, and does not do any restriction.And required thermoelectric material powder source and preparation method thereof can be got rid of etc. for SHS process, zone-melting process, machine-alloying, wet chemistry method and melt rotation and be prepared thermoelectric material method, the present invention does not do any restriction to this.Meanwhile, the described material powder preparing thermoelectric material can also prepare suspension for 3D printing by method of the present invention.
The preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing：By proportioning, thermoelectric material powder, dispersant, solvent are mixed by ball-milling method, that is, obtain the thermoelectric material powder suspension for 3D printing.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, comprises the steps：
1) thermoelectric material powder, dispersant, solvent are prepared according to proportioning, the amount of thermoelectric material powder is with respect to thermoelectric material powder, dispersant, solvent can be between 1～40% with volume percentage, and wherein dispersant can be between 5%～50% with respect to thermoelectric material powder percent by volume；
2) described thermoelectric material powder, dispersant and solvent are carried out ball milling ball milling, gained mixed liquor is the thermoelectric material powder suspension being used for 3D printing.
By such scheme, step 2) in ball-milling technology be divided into three steps, design parameter is：First, set support plate revolution as 50～100r/min, grinding pot revolution is -50～-100r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 2～5 times；Then, set support plate revolution as 200～300r/min, grinding pot revolution is -200～-300r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeat to grind 6-10 time；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, and ball milling 30 minutes suspends 15 minutes, repeats to grind 1～3 time.
By such scheme, described step 1) and step 2) between also include step 3), step 3) be：Thermoelectric material powder is carried out being dried after wet grinding, sieves.Wherein, the concrete operations of wet grinding are：Thermoelectric material powder is added mill ball and appropriate dehydrated alcohol to carry out wet grinding.During wet grinding, thermoelectric material powder, mill ball, the mass ratio (being mass ratio or volume ratio) of dehydrated alcohol are preferably 1:2:1～1.6, more specific technological parameter is：Set support plate revolution as 300r/min, grinding pot revolution is -300r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 20 times.
By such scheme, described step 3) in be dried concrete operations be：It is dried to dehydrated alcohol evaporating completely, baking temperature is preferably 90 DEG C；Described preferably 300 mesh that sieve sieve.
The present invention relates to one kind using thermoelectric material powder as solute, add the method that solvent and very small amount dispersant prepare suspension by ball-milling method.This suspension can be used as the ink used by ink-jet 3D printing, the part of printable thermo-electric device.Based on above content, on the premise of without departing from basic fundamental thought of the present invention, ordinary technical knowledge according to this area and means can also have modification, replacement or the change of multiplex form.
Compared with prior art, the invention has the beneficial effects as follows：
1st, multiple thermoelectric material powders can be prepared thermoelectric material suspension by ball-milling method by the present invention; provide a kind of simple production process, can prepare with scale hot standby thermoelectric material suspension method; in suspension, the species of additive is few and content is low, and the later stage easily removes thus ensure that the performance that thermoelectric material originally has.
2nd, the suspension prepared by the present invention can be used as the ink used by ink-jet 3D printing, function admirable, stable in properties, particle diameter as the thermoelectricity powder body of solute can control in below 45um according to the difference in shower nozzle aperture, the viscosity (viscosity of suspension) of ink can the specific requirement of different shower nozzles adjust to change by the content regulating and controlling solid content and additive according to needed for print, and subject range is wider.
Brief description
Fig. 1 is high-performance ball mill grinding tank used and support plate rotation direction schematic diagram in the embodiment of the present invention, wherein, 1- grinding pot present position, rotate in the direction of the arrow and be defined as positive direction；2- support plate, rotates in the direction of the arrow and is defined as positive direction.
Fig. 2 is step 5 in the embodiment of the present invention 1) be dried after obtained powder body FESEM figure.
Fig. 3 is the finished figure of gained powder suspension in the embodiment of the present invention 1, and wherein, left figure is state when just preparing, and right figure is the state after 7 days.
Fig. 4 is the surface texture after p-type SnTe thermoelectric arm printing shaping in application examples.
Fig. 5 is equipment overall structure schematic diagram；
Fig. 6 a is single spraying head printing equipment schematic diagram；
Fig. 6 b is the side view of Fig. 6 a；
Fig. 7 is gas-circulating system schematic diagram；
Fig. 8 is inkjet printing pattern and laser scanning zone map schematic diagram.
Specific embodiment
In order to be better understood from the present invention, present disclosure be expanded on further with reference to embodiment, but present disclosure is not limited solely to the following examples.
Embodiment 1
A kind of thermoelectric material powder suspension for 3D printing, it includes Bi2Te2.7Se0.3Thermoelectric material powder, polyethylene of dispersing agent ketopyrrolidine, solvent dehydrated alcohol, wherein thermoelectric material powder volume account for thermoelectric material powder, dispersant, the 3.58% of solvent three's cumulative volume, dispersant relative to thermoelectric material powder volume content be 11.07%.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, comprises the steps：
1) prepare Bi2Te2.7Se0.3Thermoelectric material powder, polyethylene of dispersing agent ketopyrrolidine, solvent dehydrated alcohol；
2) taking step 1) thermoelectric material powder that taken puts in high-performance ball mill, adds mill ball and appropriate dehydrated alcohol wet grinding, technological parameter is：Set support plate revolution as 300r/min, grinding pot revolution is -300r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 20 times；Thermoelectric material powder, mill ball, the mass ratio of dehydrated alcohol are 1:2:1；
3) by step 2) mixture of gained takes out and puts into the drying baker that temperature is 90 DEG C and volatilize completely to dehydrated alcohol, then cross 300 mesh sieves, obtain the powder body of drying；
4) by step 3) in the thermoelectric material powder 3.4g and dispersant (PVP) 0.0565g of gained, solvent (dehydrated alcohol) 12ml and appropriate mill ball put into and in ball grinder, carry out ball milling, technological parameter is：First, set support plate revolution as 100r/min, grinding pot revolution is -100r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 2 times；Then, set support plate revolution as 300r/min, grinding pot revolution is -300r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 6 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, and ball milling 30 minutes suspends 15 minutes, repeats to grind 1 time；Ball milling terminates rear gained mixed liquor and is the thermoelectric material powder suspension being used for 3D printing.
As can be seen from Figure 2, step 3 in the embodiment of the present invention 1) be dried after the particle diameter overwhelming majority of obtained powder body be distributed between 5-20 μm, meet the Particle size requirements of shower nozzle during ink-jet.
From the figure 3, it may be seen that the present embodiment gained powder suspension stable performance, deposit 7 days and do not produce precipitation.
Embodiment 2
A kind of thermoelectric material powder suspension for 3D printing, it includes Bi2Te2.7Se0.3Thermoelectric material powder, polyethylene of dispersing agent ketopyrrolidine, aqueous solvent, wherein, thermoelectric material powder volume account for thermoelectric material powder, dispersant, the 14.59% of solvent three's cumulative volume, dispersant with respect to powder body percent by volume be 23.92%.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, comprises the steps：
1) prepare Bi2Te2.7Se0.3Thermoelectric material powder, polyethylene of dispersing agent ketopyrrolidine, solvent dehydrated alcohol；
2) taking step 1) thermoelectric material powder that taken puts in high-performance ball mill, adds mill ball and suitable quantity of water wet grinding, technological parameter is：Set support plate revolution as 350r/min, grinding pot revolution is -350r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 20 times；Thermoelectric material powder, mill ball, the mass ratio of water are 1:2:1.5；
3) by step 2) mixture of gained takes out and puts into the drying baker that temperature is 90 DEG C and volatilize completely to water, then cross 300 mesh sieves, obtain the powder body of drying；
4) by step 3) in the thermoelectric material powder 108.2802g and dispersant (PVP) 3.9g of gained, aqueous solvent 80ml and appropriate mill ball put into and in ball grinder, carry out ball milling, technological parameter is：First, set support plate revolution as 80r/min, grinding pot revolution is -80r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 2 times；Then, set support plate revolution as 350r/min, grinding pot revolution is -350r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 7 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, and ball milling 30 minutes suspends 15 minutes, repeats to grind 1 time；Ball milling terminates rear gained mixed liquor and is the thermoelectric material powder suspension being used for 3D printing.
Embodiment 3
A kind of thermoelectric material powder suspension for 3D printing, it includes Bi2Te2.7Se0.3Thermoelectric material powder, polyethylene of dispersing agent ketopyrrolidine, solvent dehydrated alcohol, wherein, thermoelectric material powder volume account for thermoelectric material powder, dispersant, the 5.24% of solvent three's cumulative volume, dispersant relative to thermoelectric material volume content be 43.70%.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, comprises the steps：
1) prepare Bi2Te2.7Se0.3Thermoelectric material powder (all below 45 μm, wherein more than 1 μm of particle fraction can not be less than 90% to granularity, and more than 10 μm of particle fraction can not be less than 50%), polyethylene of dispersing agent ketopyrrolidine, solvent dehydrated alcohol；
2) by step 1) in the thermoelectric material powder 28.0002g that taken put into and in ball grinder, carry out ball milling with dispersant (PVP) 1.8400g, solvent (dehydrated alcohol) 65ml and appropriate mill ball, technological parameter is：First, set support plate revolution as 100r/min, grinding pot revolution is -100r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 2 times；Then, set support plate revolution as 300r/min, grinding pot revolution is -300r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 6 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, and ball milling 30 minutes suspends 15 minutes, repeats to grind 1 time；Ball milling terminates rear gained mixed liquor and is the thermoelectric material powder suspension being used for 3D printing.
Embodiment 4
A kind of thermoelectric material powder suspension for 3D printing, it includes SnTe thermoelectric material powder, polyethylene of dispersing agent ketopyrrolidine, solvent dehydrated alcohol, wherein, thermoelectric material powder volume account for thermoelectric material powder, dispersant, the 5.68% of solvent three's cumulative volume, dispersant with respect to powder body percent by volume be 36.76%.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, comprises the steps：
1) SnTe thermoelectric material powder, polyethylene of dispersing agent ketopyrrolidine, solvent dehydrated alcohol are prepared；
2) taking step 1) thermoelectric material powder that taken puts in high-performance ball mill, adds mill ball and appropriate dehydrated alcohol wet grinding, technological parameter is：Set support plate revolution as 360r/min, grinding pot revolution is -360r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 18 times；Thermoelectric material powder, mill ball, the mass ratio of dehydrated alcohol are 1:2:1.3；
3) by step 2) mixture of gained takes out and puts into the drying baker that temperature is 90 DEG C and volatilize completely to dehydrated alcohol, then cross 300 mesh sieves, obtain the powder body of drying；
4) by step 3) in the thermoelectric material powder 27.9992g and dispersant (PVP) 1.8399g of gained, solvent dehydrated alcohol 71ml and appropriate mill ball put into and in ball grinder, carry out ball milling, technological parameter is：First, set support plate revolution as 100r/min, grinding pot revolution is -100r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 2 times；Then, set support plate revolution as 300r/min, grinding pot revolution is -300r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 6 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, and ball milling 30 minutes suspends 15 minutes, repeats to grind 1 time；Ball milling terminates rear gained mixed liquor and is the thermoelectric material powder suspension being used for 3D printing.
Embodiment 5
A kind of thermoelectric material powder suspension for 3D printing, it includes SnTe thermoelectric material powder, dispersant benzoic acid, solvent dehydrated alcohol, wherein, thermoelectric material powder volume account for thermoelectric material powder, dispersant, the 7.00% of solvent three's cumulative volume, dispersant with respect to powder body percent by volume be 48.03%.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, comprises the steps：
1) SnTe thermoelectric material powder, dispersant benzoic acid, solvent dehydrated alcohol are prepared；
2) taking step 1) thermoelectric material powder that taken puts in high-performance ball mill, adds mill ball and appropriate dehydrated alcohol wet grinding, technological parameter is：Set support plate revolution as 360r/min, grinding pot revolution is -360r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 18 times；Thermoelectric material powder, mill ball, the mass ratio of dehydrated alcohol are 1:2:1.4；
3) by step 2) mixture of gained takes out and puts into the drying baker that temperature is 90 DEG C and volatilize completely to dehydrated alcohol, and then 300 mesh sieve, and obtain the powder body of drying；
4) by step 3) in the thermoelectric material powder 20g and benzoic acid 1.9g of gained, solvent dehydrated alcohol 40ml and appropriate mill ball put into and in ball grinder, carry out ball milling, technological parameter is：First, set support plate revolution as 75r/min, grinding pot revolution is -75r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 2 times；Then, set support plate revolution as 360r/min, grinding pot revolution is -360r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 7 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, and ball milling 30 minutes suspends 15 minutes, repeats to grind 2 times；Ball milling terminates rear gained mixed liquor and is the thermoelectric material powder suspension being used for 3D printing.
Embodiment 6
A kind of thermoelectric material powder suspension for 3D printing, it is water including SnTe thermoelectric material powder, dispersant PEG-4000, solvent, wherein, thermoelectric material powder volume account for thermoelectric material powder, dispersant, the 7.68% of solvent three's cumulative volume, dispersant with respect to powder body percent by volume be 28.07%.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, comprises the steps：
1) SnTe thermoelectric material powder, dispersant PEG-4000, aqueous solvent are prepared；
2) taking step 1) thermoelectric material powder that taken puts in high-performance ball mill, adds mill ball and appropriate dehydrated alcohol wet grinding, technological parameter is：Set support plate revolution as 310r/min, grinding pot revolution is -310r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 17 times；Thermoelectric material powder, mill ball, the mass ratio of water are 1:2:1.6；
3) by step 2) mixture of gained takes out and puts into the drying baker that temperature is 90 DEG C and volatilize completely to dehydrated alcohol, and then 300 mesh sieve, and obtain the powder body of drying；
4) by step 3) in the thermoelectric material powder 30g and PEG-4000 1.5g of gained and aqueous solvent 55ml and appropriate mill ball put into and in ball grinder, carry out ball milling.Technological parameter is：First, set support plate revolution as 60r/min, grinding pot revolution is -60r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 1 time；Then, set support plate revolution as 310r/min, grinding pot revolution is -310r/min, relative rate is -1, ball milling suspends 15 minutes in 30 minutes, repeats to grind 7 times；Resetting support plate revolution is 100r/min, and grinding pot revolution is -100r/min, and relative rate is -1, and ball milling 30 minutes suspends 15 minutes, repeats to grind 3 times；Ball milling terminates rear gained mixed liquor and is the thermoelectric material powder suspension being used for 3D printing.
Application examples：
The 3D printing Apparatus for () and method therefor of a kind of combination inkjet printing and selective laser fusion technology is provided, it is possible to achieve thermoelectric material powder suspension of the present invention is used for the technical scheme of 3D printing in the present invention.But the method that suspension of the present invention realizes 3D printing is not limited to equipment provided below, and the equipment of any technical scheme being capable of described in claims of the present invention could be used for the present invention, and the present invention is without limitation.
A kind of combination inkjet printing and the 3D printing Apparatus for () and method therefor of selective laser fusion technology, specific as follows：
(1) the 3D printing equipment of a kind of combination inkjet printing and selective laser fusion technology, including storage tank, forming cavity and gas-recycling plant, described shaping top of chamber is provided with laser light incident window, described molding intracavity is provided with inkjet-printing device, described inkjet-printing device includes substrate and ink jet-print head, described storage tank is used for storing ink, and by providing ink to described ink jet-print head, described gas-recycling plant includes seal cavity, it is provided with filter layer inside seal cavity, drying layer and circulating fan, it is tightly connected with described forming cavity in described seal cavity.
Further, in above-mentioned equipment, described inkjet-printing device also includes the base with x to displacement platform, described x places substrate on displacement platform, support to displacement platform is arranged with y on base, y fixes z to displacement platform on displacement platform, and z fixes ink jet-print head on displacement platform, and described ink jet-print head is located at surface.
Further, in above-mentioned equipment, below described substrate, it is provided with panel heater.
Further, in above-mentioned equipment, described molding cavity wall is provided with the solvent gas concentration detector that the content to the volatile solvent in gas in cavity is monitored.
Further, in above-mentioned equipment, described molding cavity wall is provided with the water vapour content detector that the vapour content in gas in cavity is monitored.
(2) printing technology of the 3D printing equipment of above-mentioned combination inkjet printing and selective laser melting, comprises the steps of：
A. the ink in storage tank is injected in ink jet-print head；
B. ink jet-print head single layer pattern needed for printing on substrate by the way of inkjet printing；
C. the temperature of control base board, is made the solvent in ink quickly volatilize, is rapidly removed by the drying layer in gas-recycling plant, and the working gas being dried is returned to inside molding cavity；
D. after surface is removed, substrate returns to initial point to ink jet-print head, and the pattern on substrate carries out molding and connection by precinct laser melting, obtains monolayer densified thin layer material；
E. repeat above procedure and obtain multiple dense block materials.
Further, in above-mentioned technique, molding intracavity working gas is Ar or N2；
Further, in above-mentioned technique, after step c, after the water content of molding intracavity working gas is reduced to below 100ppm, ability execution step d.
Further, in above-mentioned technique, after step c, after the oxygen content of molding intracavity working gas is reduced to below 100ppm, ability execution step d.
(3) combine accompanying drawing, the 3D printing equipment illustrating this with reference to inkjet printing and selective laser fusion technology specifically includes forming cavity 1, storage tank 3, gas-circulating system 4 and solvent gas concentration detector 5 (Fig. 5) for storing ink.
An inkjet-printing device 2 is placed, this part can move up and down in overall becoming in cavity 1 in forming cavity 1.Inkjet-printing device 2 (Fig. 6 a, Fig. 6 b) comprises the base 21 of the displacement platform of a band x direction motion, and this x is sequentially placed a panel heater 26 and substrate 25 on displacement platform.One support 22 is arranged on base, support 22 carries the displacement platform that can move in the y-direction, this y fixes a displacement platform 23 that can move in the z-direction again on displacement platform, this z fixes an ink jet-print head 24 on displacement platform 23, ink jet-print head 24 is located above substrate 25.
Ink in storage tank 3 can be by the ink jet-print head 24 of pipeline to molding intracavity.Gas-circulating system 4 (Fig. 7) comprises a seal cavity 31, and cavity top is provided with an air inlet 36, and side is provided with an air outlet 32, and inside cavity is provided with a drying layer 35, filter layer 34 and circulating fan 33 from top to bottom.
Its method of work is：Ink in storage tank 3 is transported in ink jet-print head 24, ink injection is out deposited to substrate 25 surface by ink jet-print head 24, first layer pattern is printed on substrate 25 by the relative motion of shower nozzle 24 and substrate 25, the temperature control of substrate 25 is below the boiling point of solvent, aqueous solvent is made quickly to volatilize, vapor and working gas Ar or N2Mixing is removed by being adsorbed by drying layer 35 after gas-recycling plant 4.After ink dried, substrate 25 returns to initial point.Using solvent gas concentration water finder 5 detect mixed gas in vapor concentration, when its content is in 100ppm, using selective laser melting technique substrate 25 on powder layer material be scanned and curing molding and and substrate 25 connect.Repeat above procedure and obtain multiple dense block materials.In the above process, the scope 42 of selective laser smelting process scanning is within the scope 41 of inkjet printing (Fig. 8).
Using above-mentioned 3D printing Apparatus for () and method therefor, SnTe powder suspension prepared by embodiment 4 is used for 3D printing and quickly prepares p-type SnTe thermoelectric arm, comprises the steps：
1) SnTe powder suspension prepared by embodiment 4 is placed in the ink as inkjet printing in storage tank, the ink in storage tank is transported in ink jet printing head under the effect of the pressure；Prepare the Al that thickness is 1mm2O3Ceramic wafer is placed and fixing on printing substrate；Molding cavity forvacuum 5 minutes to selective laser melting plant, then adopts Ar gas backfill cavity to normal pressure, keeps cavity water oxygen content in below 100ppm, and basal plate preheating to 80 DEG C and is incubated 10 minutes simultaneously；
2) the p-type thermoelectric material powder in storage tank is spread over Al2O3Ceramic plate surface, is then scanned according to the thermo-electric device thermoelectric arm size of design and distribution using laser, is printed as p-type thermoelectric arm and N-shaped thermoelectric arm；Wherein, when printing thermoelectric arm, powdering thickness is 50 microns, and laser scan rate is chosen as 50mm/s, and laser power is chosen as 50W；The print procedure repeating above thermoelectric arm is up to desired height.
Fig. 4 is for the surface texture after the thermoelectric arm laser scanning molding of p-type SnTe it can be seen that the surface after laser melting is very smooth.
Above-described embodiment all can make the suspension of thermoelectric material, and due to the difference of solid content, dispersant, the stability of suspension can be variant, but the ink printed thermo-electric device part as ink-jet 3D printing, and the stability of example all can meet requirement.For solid content, dispersant addition, the composition of powder body, the content of solvent is different from species, also can achieve technical scheme, embodiment numerous to list herein.
The above be only the preferred embodiment of the present invention it is noted that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these broadly fall into protection scope of the present invention.
Claims (10)
1. a kind of thermoelectric material powder suspension for 3D printing is it is characterised in that it includes thermoelectric material powder, dispersion
Agent, solvent.
2. a kind of thermoelectric material powder suspension for 3D printing according to claim 1 is it is characterised in that described
Solid content for the thermoelectric material powder suspension of 3D printing is calculated as 1～40% with percent by volume, wherein dispersant with respect to
Thermoelectricity powder body percent by volume is 5%～50%.
3. a kind of thermoelectric material powder suspension for 3D printing according to claim 1 is it is characterised in that described
, in below 45um, wherein more than 1 μm of particle fraction can not be less than 90%, more than 10 μm for the granularity of thermoelectric material powder
Particle fraction can not be less than 50%.
4. a kind of thermoelectric material powder suspension for 3D printing according to claim 1 is it is characterised in that described
Dispersant is one of Polyvinylpyrrolidone, benzoic acid or Polyethylene Glycol or several mixture in any proportion.
5. a kind of thermoelectric material powder suspension for 3D printing according to claim 1 is it is characterised in that described
Solvent is one of water, dehydrated alcohol, acetone or several mixture in any proportion.
6. a kind of preparation method of the thermoelectric material powder suspension for 3D printing is it is characterised in that by thermoelectric material powder
Body, dispersant, solvent are mixed by ball-milling method, that is, obtain the thermoelectric material powder suspension for 3D printing.
7. the preparation method of a kind of thermoelectric material powder suspension for 3D printing according to claim 6, it is special
Levy and be to comprise the steps：
1) thermoelectric material powder, dispersant, solvent are prepared according to proportioning, wherein thermoelectric material powder volume accounts for thermoelectric material powder
Body, dispersant, the 1～40% of solvent three's cumulative volume, the volume of dispersant is the 5～50% of the volume of thermoelectric material powder；
2) described thermoelectric material powder, dispersant and solvent are carried out ball milling ball milling, gained mixed liquor is and beats for 3D
The thermoelectric material powder suspension of print.
8. the preparation method of a kind of thermoelectric material powder suspension for 3D printing according to claim 7, it is special
Levy and be step 2) in the parameter of ball-milling technology be：Support plate revolution is 50～600r/min ball milling more than 30 minutes.
9. the preparation method of a kind of thermoelectric material powder suspension for 3D printing according to claim 7, it is special
Levy and be described step 1) and step 2) between also include carrying out being dried after wet grinding by thermoelectric material powder, the step sieved.
10. the suspension described in claim 1 is as the application of 3D printing ink.
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