CN106378447B - A kind of thermoelectric material powder suspension and preparation method thereof for 3D printing - Google Patents
A kind of thermoelectric material powder suspension and preparation method thereof for 3D printing Download PDFInfo
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- CN106378447B CN106378447B CN201610125086.XA CN201610125086A CN106378447B CN 106378447 B CN106378447 B CN 106378447B CN 201610125086 A CN201610125086 A CN 201610125086A CN 106378447 B CN106378447 B CN 106378447B
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- 239000000463 material Substances 0.000 title claims abstract description 135
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- 238000010146 3D printing Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 44
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- 238000000034 method Methods 0.000 claims abstract description 29
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- 238000000227 grinding Methods 0.000 claims description 62
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001238 wet grinding Methods 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
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- 239000002202 Polyethylene glycol Substances 0.000 claims 1
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- 239000003125 aqueous solvent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 150000004040 pyrrolidinones Chemical class 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
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- 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
- 241000921268 Selago corymbosa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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- 150000001336 alkenes Chemical class 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
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The present invention provides a kind of thermoelectric material powder suspension for 3D printing, it is characterised in that it includes thermoelectric material powder, dispersing agent, solvent.The suspension can be used as ink-jet 3D printing ink used; it can be used as printing the component of thermoelectric material device; wherein the viscosity of ink can be adjusted according to the specific requirement of spray head needed for different printings by the content of regulation solid content and additive; the partial size of thermoelectricity powder can be according to the different controls in spray head aperture in 45um or less; the solid content of suspension is calculated as 1~40% with percent by volume; wherein dispersing agent is 5%~50% relative to powder percent by volume; this method preparation process is simple, has the prospect of large-scale production.
Description
Technical field
The thermoelectric material powder suspension and preparation method thereof that the present invention relates to a kind of for 3D printing, belongs to thermoelectric material
Preparation technical field.
Background technique
Thermoelectric material is that one kind can be directly realized by the functional material directly converted between electric energy and thermal energy, is imitated using Seebeck
Thermal energy should be converted into electric energy, realize thermo-electric generation, paltie effect can also be used, electric energy is converted into thermal energy,
Realize temperature-difference refrigerating.
The preparation of Conventional thermoelectric device is realized by way of subtracting material manufacture.Firstly, preparing institute by simple substance raw material
Need material powder, after powder be put into mold obtain thermoelectric material block by means such as sintering, then by block cutting at institute
Shape is needed, then block is connected with electrode material.The device fabrication process of this complex process not only results in raw material
Waste, and the device with labyrinth and the microdevice with fine structure can not be prepared.
In recent years, extensive attention of the increases material manufacturing technology including ink-jet 3D printing by domestic and international researcher.Spray
Black 3D printing be uniform drop is ejected by spray head, while spray head or substrate according to the route of design by dimensionally moving
It is dynamic, so that drop, by line to face again to body, is accurately deposited on substrate by putting to line and quickly realizes beating for three-dimensional structure
Print.This manufacturing technology with manufacturing process without waste of material, complicated shape or device with fine structure can be prepared, can make
The advantages that carrying out the preparation of multiple functions structure member simultaneously using a variety of inks with multiple spray heads.For thermo-electric device,
It can be achieved to print while two kinds of materials of N-type and p-type, 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 to print the allotment of ink used.Ink will have well
Stability, the size of diameter of particle will be distributed in reasonable range, and partial size is easy greatly very much to block spray head, and partial size is too small not
Conducive to the densification of device.Solid phase particles size in the ink of existing inkjet printing is respectively less than 1 μm, is unfavorable for thermoelectricity material
The later period of material densifies.Meanwhile in order to make the device printed that there is good thermoelectricity capability, the additive kind being added in ink
Class will be lacked as far as possible, and the amount of addition is low as far as possible, and the later period easily removes, and be easy to the densification of printed product.Ink droplet is spraying
During penetrating, it is necessary first to overcome the absorption of spray head capillary force, could smoothly spray.Secondly, the formula of ink can direct shadow
Ring the appearance of extra satellite point in the wetability and course of injection of ink droplet and substrate contact.In addition, ink droplet after matrix deposition by
To the effect of surface tension gradient, so that there is coffee ring effect by center directional migration around in solute in ink.Performance is excellent
Good ink can be flowed by adjusting the Ma Langgeni of its viscosity and effect of surface tension ink droplet on matrix, to control coffee
The effect of coffee ring prints the finished product of function admirable.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of for 3D in view of the deficiency of the prior art
Thermoelectric material powder suspension of printing and preparation method thereof, the type of additive is few in suspension and content is low, and the later period easily goes
It removes, the performance that thermoelectric material originally has has been effectively ensured.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A kind of thermoelectric material powder suspension for 3D printing comprising thermoelectric material powder, dispersing agent, solvent.
According to the above scheme, the solid content of the thermoelectric material powder suspension for being used for 3D printing can be with volume percentage
Between 1~40%, wherein dispersing agent can be between 5%~50% relative to thermoelectric material powder percent by volume.The suspension
Solid content=V of liquid1/(V1+V2+V3), dispersing agent is with respect to thermoelectric material powder volume content=V3/V1, wherein V1For thermoelectricity material
Feed powder body volume, is calculated, V by powder quality and density of material2For solvent volume, V3For dispersing agent volume.
According to the above scheme, the granularity of the thermoelectric material powder is at 45 μm hereinafter, wherein 1 μm or more of particle fraction cannot
Particle fraction less than 90%, 10 μm or more cannot be less than 50%.
According to the above scheme, the dispersing agent is in polyvinylpyrrolidone (PVP), benzoic acid or polyethylene glycol-400 etc.
One or several kinds of mixtures in any proportion.
According to the above scheme, the solvent be one of liquid such as water, dehydrated alcohol, acetone or it is several in any proportion
Mixture.
According to the above scheme, the 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.；The thermoelectric material powder is N-shaped
Thermoelectric compound can be selected from Bi2Te3-xSex、SnTe、n-Co4Sb12-xTex、Mg2Si1-xSnx, appointing in ZrNiSn and PbS etc.
It anticipates one kind.Technical solution of the present invention is suitable for any system thermoelectric material powder, herein only for example, not doing any limit
System.And required thermoelectric material powder source and preparation method thereof can for SHS process, zone-melting process, machine-alloying,
Wet chemistry method and melt rotation get rid of etc. and to prepare thermoelectric material method, and the present invention does not do any restrictions to this.Meanwhile described preparing thermoelectricity
The material powder of material the method can also prepare suspension for 3D printing through the invention.
The preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing: according to the ratio by thermoelectric material powder, point
Powder, solvent are mixed by ball-milling method to get the thermoelectric material powder suspension for 3D printing is arrived.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, includes the following steps:
1) prepare thermoelectric material powder, dispersing agent, solvent according to the proportion, the amount of thermoelectric material powder is relative to thermoelectric material
Powder, dispersing agent, solvent can be between 1~40% with volume percentage, and wherein dispersing agent is relative to thermoelectric material powder
Percent by volume can be between 5%~50%；
2) thermoelectric material powder, dispersing agent and solvent are subjected to ball milling ball milling, gained mixed liquor is to be used for 3D
The thermoelectric material powder suspension of printing.
According to the above scheme, ball-milling technology is divided into three steps, design parameter in step 2) are as follows: firstly, set support plate revolution as
50~100r/min, grinding pot revolution are -50~-100r/min, and relative rate is -1, suspend 15 minutes within ball milling 30 minutes, repeat
Grinding 2~5 times；Then, support plate revolution is set as 200~300r/min, and grinding pot revolution is -200~-300r/min, phase
It is -1 to rate, suspends 15 minutes within ball milling 30 minutes, repeat grinding 6-10 times；Resetting support plate revolution is 50r/min, grinding pot
Revolution is -50r/min, and relative rate is -1, ball milling 30 minutes, suspends 15 minutes, repeats grinding 1~3 time.
It according to the above scheme, further include step 3), step 3) between the step 1) and step 2) are as follows: by thermoelectric material powder
Dry, sieving after progress wet-milling.Wherein, the concrete operations of wet-milling are as follows: mill ball and appropriate anhydrous is added in thermoelectric material powder
Ethyl alcohol carries out wet-milling.When wet-milling, thermoelectric material powder, mill ball, dehydrated alcohol mass ratio (being mass ratio or volume ratio)
Preferably 1:2:1~1.6, more specific technological parameter are as follows: set support plate revolution as 300r/min, grinding pot revolution is -300r/
Min, relative rate are -1, suspend 15 minutes within ball milling 30 minutes, repeat grinding 20 times.
According to the above scheme, concrete operations dry in the step 3) are as follows: dry to dehydrated alcohol evaporating completely, dry temperature
Preferably 90 DEG C of degree；The sieving is preferably the sieving of 300 mesh.
The present invention relates to a kind of using thermoelectric material powder as solute, and solvent is added and minute quantity dispersing agent passes through ball-milling method
The method for preparing suspension.This suspension can be used as ink used in ink-jet 3D printing, can print the component of thermo-electric device.More than
Based on content, under the premise of not departing from basic fundamental thought of the present invention, according to the ordinary technical knowledge and means of this field
Can also there are the modification, replacement or change of multiplex form.
Compared with prior art, the beneficial effects of the present invention are:
1, a variety of thermoelectric material powders can be prepared thermoelectric material suspension by ball-milling method by the present invention, provide a kind of life
Production. art is simple, can the hot standby thermoelectric material suspension of prepare with scale method, the type of additive is few in suspension and content
Low, the later period easily removes to ensure that the performance that thermoelectric material originally has.
2, the suspension prepared by the present invention can be used as ink-jet 3D printing ink used, and function admirable, property are stablized,
The partial size of thermoelectricity powder as solute can be controlled in 45um according to the different of spray head aperture hereinafter, the viscosity (suspension of ink
Viscosity) can be adjusted according to the specific requirement of different spray heads needed for printing by the content of regulation solid content and additive to change
Become, adaptation range is wider.
Detailed description of the invention
Fig. 1 is high-performance ball mill grinding tank and support plate rotation direction schematic diagram used in the embodiment of the present invention, wherein
1- grinding pot present position, rotation is defined as positive direction in the direction of the arrow；2- support plate, rotation is defined as pros in the direction of the arrow
To.
Fig. 2 is that obtained powder FESEM schemes after step 5) drying in the embodiment of the present invention 1.
Fig. 3 is the finished figure of gained powder suspension in the embodiment of the present invention 1, wherein left figure is shape when just preparing
State, right figure are the state after 7 days.
Fig. 4 is the surface texture in application examples after p-type SnTe thermoelectric arm printing shaping.
Fig. 5 is equipment overall structure schematic diagram；
Fig. 6 a is single nozzle 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 better understand the present invention, below with reference to the embodiment content that the present invention is further explained, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of thermoelectric material powder suspension for 3D printing comprising Bi2Te2.7Se0.3Thermoelectric material powder, dispersion
Agent polyvinylpyrrolidone, solvent absolute ethyl alcohol, wherein thermoelectric material powder volume accounts for thermoelectric material powder, dispersing agent, solvent
The 3.58% of three's total volume, dispersing agent are 11.07% with respect to the volume content of thermoelectric material powder.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, includes the following steps:
1) prepare Bi2Te2.7Se0.3Thermoelectric material powder, polyethylene of dispersing agent pyrrolidones, solvent absolute ethyl alcohol；
2) thermoelectric material powder for taking step 1) to be taken is put into high-performance ball mill, and mill ball and appropriate anhydrous second is added
Alcohol wet-milling, technological parameter are as follows: support plate revolution is set as 300r/min, grinding pot revolution is -300r/min, and relative rate is -1,
Suspend 15 minutes within ball milling 30 minutes, repeats grinding 20 times；Thermoelectric material powder, mill ball, dehydrated alcohol mass ratio be 1:2:
1；
3) the resulting mixture taking-up of step 2) is put into drying box at a temperature of 90 °C to volatilize completely to dehydrated alcohol, so
300 meshes are crossed afterwards, obtain dry powder；
4) by thermoelectric material powder 3.4g obtained in step 3) and dispersing agent (PVP) 0.0565g, solvent (dehydrated alcohol)
12ml and appropriate mill ball, which are put into ball grinder, carries out ball milling, technological parameter are as follows: firstly, setting support plate revolution as 100r/
Min, grinding pot revolution are -100r/min, and relative rate is -1, suspend 15 minutes within ball milling 30 minutes, repeat grinding 2 times；Then, if
Determining support plate revolution is 300r/min, and grinding pot revolution is -300r/min, and relative rate is -1, suspends 15 minutes within ball milling 30 minutes,
Repeat grinding 6 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, ball milling 30
Minute, suspend 15 minutes, repeats grinding 1 time；Gained mixed liquor is the thermoelectric material powder for being used for 3D printing after ball milling
Suspension.
As can be seen from Figure 2, the partial size overwhelming majority of obtained powder is distributed in after step 3) is dry in the embodiment of the present invention 1
Between 5-20 μm, the Particle size requirements of spray head when meeting ink-jet.
From the figure 3, it may be seen that powder suspension performance obtained by the present embodiment is stablized, storage does not generate precipitating in 7 days.
Embodiment 2
A kind of thermoelectric material powder suspension for 3D printing comprising Bi2Te2.7Se0.3Thermoelectric material powder, dispersion
Agent polyvinylpyrrolidone, aqueous solvent, wherein it is total that thermoelectric material powder volume accounts for thermoelectric material powder, dispersing agent, solvent three
The 14.59% of volume, dispersing agent are 23.92% relative to powder percent by volume.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, includes the following steps:
1) prepare Bi2Te2.7Se0.3Thermoelectric material powder, polyethylene of dispersing agent pyrrolidones, solvent absolute ethyl alcohol；
2) thermoelectric material powder for taking step 1) to be taken is put into high-performance ball mill, and mill ball and appropriate water-wet is added
Mill, technological parameter are as follows: set support plate revolution as 350r/min, grinding pot revolution is -350r/min, and relative rate is -1, ball milling
Suspend 15 minutes within 30 minutes, repeats grinding 20 times；Thermoelectric material powder, mill ball, water mass ratio be 1:2:1.5；
3) the resulting mixture taking-up of step 2) is put into drying box at a temperature of 90 °C to volatilize completely to water, then mistake
300 meshes obtain dry powder；
4) by thermoelectric material powder 108.2802g obtained in step 3) and dispersing agent (PVP) 3.9g, aqueous solvent 80ml and
Appropriate mill ball, which is put into ball grinder, carries out ball milling, technological parameter are as follows: firstly, set support plate revolution as 80r/min, grinding pot
Revolution is -80r/min, and relative rate is -1, suspends 15 minutes within ball milling 30 minutes, repeats grinding 2 times；Then, setting support plate turns
Number is 350r/min, and grinding pot revolution is -350r/min, and relative rate is -1, suspends 15 minutes within ball milling 30 minutes, repeats grinding 7
It is secondary；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, ball milling 30 minutes, is suspended
15 minutes, repeat grinding 1 time；Gained mixed liquor is the thermoelectric material powder suspension for being used for 3D printing after ball milling.
Embodiment 3
A kind of thermoelectric material powder suspension for 3D printing comprising Bi2Te2.7Se0.3Thermoelectric material powder, dispersion
Agent polyvinylpyrrolidone, solvent absolute ethyl alcohol, wherein thermoelectric material powder volume accounts for thermoelectric material powder, dispersing agent, solvent
The 5.24% of three's total volume, dispersing agent are 43.70% with respect to thermoelectric material volume content.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, includes the following steps:
1) prepare Bi2Te2.7Se0.3(granularity is at 45 μm hereinafter, wherein 1 μm or more of particle fraction for thermoelectric material powder
Cannot be less than 90%, 10 μm or more of particle fraction cannot less than 50%), polyethylene of dispersing agent pyrrolidones, the anhydrous second of solvent
Alcohol；
2) the thermoelectric material powder 28.0002g taken in step 1) and dispersing agent (PVP) 1.8400g, solvent is (anhydrous
Ethyl alcohol) 65ml and appropriate mill ball be put into ball grinder and carry out ball milling, technological parameter are as follows: firstly, set support plate revolution as
100r/min, grinding pot revolution are -100r/min, and relative rate is -1, suspend 15 minutes within ball milling 30 minutes, repeat grinding 2 times；So
Afterwards, support plate revolution is set as 300r/min, and grinding pot revolution is -300r/min, and relative rate is -1, pause 15 in ball milling 30 minutes
Minute, repeat grinding 6 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, ball
Mill 30 minutes suspends 15 minutes, repeats grinding 1 time；Gained mixed liquor is the thermoelectric material for being used for 3D printing after ball milling
Powder suspension.
Embodiment 4
A kind of thermoelectric material powder suspension for 3D printing comprising the poly- second of SnTe thermoelectric material powder, dispersing agent
Alkene pyrrolidone, solvent absolute ethyl alcohol, wherein thermoelectric material powder volume accounts for thermoelectric material powder, dispersing agent, solvent three
The 5.68% of total volume, dispersing agent are 36.76% relative to powder percent by volume.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, includes the following steps:
1) prepare SnTe thermoelectric material powder, polyethylene of dispersing agent pyrrolidones, solvent absolute ethyl alcohol；
2) thermoelectric material powder for taking step 1) to be taken is put into high-performance ball mill, and mill ball and appropriate anhydrous second is added
Alcohol wet-milling, technological parameter are as follows: support plate revolution is set as 360r/min, grinding pot revolution is -360r/min, and relative rate is -1,
Suspend 15 minutes within ball milling 30 minutes, repeats grinding 18 times；Thermoelectric material powder, mill ball, dehydrated alcohol mass ratio be 1:2:
1.3；
3) the resulting mixture taking-up of step 2) is put into drying box at a temperature of 90 °C to volatilize completely to dehydrated alcohol, so
300 meshes are crossed afterwards, obtain dry powder；
4) by thermoelectric material powder 27.9992g obtained in step 3) and dispersing agent (PVP) 1.8399g, the anhydrous second of solvent
Alcohol 71ml and appropriate mill ball, which are put into ball grinder, carries out ball milling, technological parameter are as follows: firstly, setting support plate revolution as 100r/
Min, grinding pot revolution are -100r/min, and relative rate is -1, suspend 15 minutes within ball milling 30 minutes, repeat grinding 2 times；Then, if
Determining support plate revolution is 300r/min, and grinding pot revolution is -300r/min, and relative rate is -1, suspends 15 minutes within ball milling 30 minutes,
Repeat grinding 6 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, ball milling 30
Minute, suspend 15 minutes, repeats grinding 1 time；Gained mixed liquor is the thermoelectric material powder for being used for 3D printing after ball milling
Suspension.
Embodiment 5
A kind of thermoelectric material powder suspension for 3D printing comprising SnTe thermoelectric material powder, dispersing agent benzene first
Acid, solvent absolute ethyl alcohol, wherein thermoelectric material powder volume accounts for thermoelectric material powder, dispersing agent, solvent three's total volume
7.00%, dispersing agent is 48.03% relative to powder percent by volume.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, includes the following steps:
1) prepare SnTe thermoelectric material powder, dispersing agent benzoic acid, solvent absolute ethyl alcohol；
2) thermoelectric material powder for taking step 1) to be taken is put into high-performance ball mill, and mill ball and appropriate anhydrous second is added
Alcohol wet-milling, technological parameter are as follows: support plate revolution is set as 360r/min, grinding pot revolution is -360r/min, and relative rate is -1,
Suspend 15 minutes within ball milling 30 minutes, repeats grinding 18 times；Thermoelectric material powder, mill ball, dehydrated alcohol mass ratio be 1:2:
1.4；
3) the resulting mixture taking-up of step 2) is put into drying box at a temperature of 90 °C to volatilize completely to dehydrated alcohol, so
300 mesh are sieved afterwards, obtain dry powder；
4) by thermoelectric material powder 20g obtained in step 3) and benzoic acid 1.9g, solvent absolute ethyl alcohol 40ml and in right amount
Mill ball, which is put into ball grinder, carries out ball milling, technological parameter are as follows: firstly, set support plate revolution as 75r/min, grinding pot revolution
For -75r/min, relative rate is -1, suspends 15 minutes within ball milling 30 minutes, repeats grinding 2 times；Then, set support plate revolution as
360r/min, grinding pot revolution are -360r/min, and relative rate is -1, suspend 15 minutes within ball milling 30 minutes, repeat grinding 7 times；
Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, and relative rate is -1, ball milling 30 minutes, suspends 15 points
Clock repeats grinding 2 times；Gained mixed liquor is the thermoelectric material powder suspension for being used for 3D printing after ball milling.
Embodiment 6
A kind of thermoelectric material powder suspension for 3D printing, including the poly- second two of SnTe thermoelectric material powder, dispersing agent
Alcohol -400, solvent are water, wherein thermoelectric material powder volume accounts for thermoelectric material powder, dispersing agent, solvent three's total volume
7.68%, dispersing agent is 28.07% relative to powder percent by volume.
Preferably, the preparation method of the above-mentioned thermoelectric material powder suspension for 3D printing, includes the following steps:
1) prepare SnTe thermoelectric material powder, dispersing agent polyethylene glycol-400, aqueous solvent；
2) thermoelectric material powder for taking step 1) to be taken is put into high-performance ball mill, and mill ball and appropriate anhydrous second is added
Alcohol wet-milling, technological parameter are as follows: support plate revolution is set as 310r/min, grinding pot revolution is -310r/min, and relative rate is -1,
Suspend 15 minutes within ball milling 30 minutes, repeats grinding 17 times；Thermoelectric material powder, mill ball, water mass ratio be 1:2:1.6；
3) the resulting mixture taking-up of step 2) is put into drying box at a temperature of 90 °C to volatilize completely to dehydrated alcohol, so
300 mesh are sieved afterwards, obtain dry powder；
4) it by thermoelectric material powder 30g obtained in step 3) and polyethylene glycol-400 1.5g and aqueous solvent 55ml and fits
Amount mill ball, which is put into ball grinder, carries out ball milling.Technological parameter are as follows: firstly, setting support plate revolution as 60r/min, grinding pot turns
Number is -60r/min, and relative rate is -1, suspends 15 minutes within ball milling 30 minutes, repeats grinding 1 time；Then, support plate revolution is set
For 310r/min, grinding pot revolution is -310r/min, and relative rate is -1, suspends 15 minutes within ball milling 30 minutes, repeats grinding 7 times；
Resetting support plate revolution is 100r/min, and grinding pot revolution is -100r/min, and relative rate is -1, ball milling 30 minutes, suspends 15
Minute, repeat grinding 3 times；Gained mixed liquor is the thermoelectric material powder suspension for being used for 3D printing after ball milling.
Application examples:
The 3D printing device and method thereof of a kind of combination inkjet printing and selective laser fusion technology are provided in the present invention,
Technical solution of the thermoelectric material powder suspension of the present invention for 3D printing may be implemented.But suspension of the present invention
The method that liquid realizes 3D printing is not limited to equipment provided below, any to can be realized recorded in claims of the present invention
The equipment of technical solution could be used for the present invention, the present invention is without limitation.
A kind of 3D printing device and method thereof of combination inkjet printing and 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, the forming cavity top are equipped with laser light incident window, are equipped with inkjet-printing device, institute in the forming cavity
Stating inkjet-printing device includes substrate and inkjet print head, and the storage tank is for storing ink, and by providing ink to described
Inkjet print head, the gas-recycling plant include seal cavity, are equipped with filter layer, drying layer and circulated air inside seal cavity
Machine is tightly connected in the seal cavity with the forming cavity.
Further, in above-mentioned equipment, the inkjet-printing device further includes the pedestal with x to displacement platform, the x to
It places substrate on displacement platform, is arranged with y on pedestal to the bracket of displacement platform, y fixes z on displacement platform to displacement platform, and z is to displacement
Inkjet print head is fixed on platform, the inkjet print head is located above substrate.
Further, in above-mentioned equipment, panel heater is equipped with below the substrate.
Further, in above-mentioned equipment, the molding cavity wall is equipped with to the volatile solvent in gas in cavity
The solvent gas concentration detector that is monitored of content.
Further, in above-mentioned equipment, the molding cavity wall be equipped with to the vapour content in gas in cavity into
The water vapour content detector of row monitoring.
(2) printing technology of above-mentioned combination inkjet printing and the 3D printing equipment of selective laser melting includes following step
It is rapid:
A. the ink in storage tank is injected into inkjet print head；
B. single layer pattern needed for inkjet print head is printed on substrate by the way of inkjet printing；
C. the temperature of control base board makes the solvent in ink quickly volatilize, and passes through the drying layer in gas-recycling plant
It rapidly removes, dry working gas is returned to inside molding cavity；
D. after inkjet print head is removed above substrate, substrate returns to origin, and the pattern on substrate is molten by precinct laser
Row molding and connection are circulated, single layer densified thin layer material is obtained；
E. it repeats above procedure and obtains multiple dense block materials.
Further, in above-mentioned technique, working gas is Ar or N in forming cavity2；
Further, in above-mentioned technique, after step c, the water content of working gas is reduced to 100ppm in forming cavity
After below, step d is just executed.
Further, in above-mentioned technique, after step c, the oxygen content of working gas is reduced to 100ppm in forming cavity
After below, step d is just executed.
(3) in conjunction with attached drawing, this is illustrated in conjunction with the 3D printing equipment of inkjet printing and selective laser fusion technology tool
Body includes forming cavity 1, the storage tank 3 for storing ink, gas-circulating system 4 and the (figure of solvent gas concentration detector 5
5)。
An inkjet-printing device 2 is placed in forming cavity 1, which can move up and down in overall at cavity 1.Inkjet printing
Device 2 (Fig. 6 a, Fig. 6 b) includes the pedestal 21 of a displacement platform with the movement of the direction x, which is sequentially placed a plate on displacement platform
Heater 26 and substrate 25.One bracket 22 is set on pedestal, and with the displacement platform that can be moved in the y-direction on bracket 22, the y is to position
A displacement platform 23 that can be moved in the z-direction is fixed in moving stage again, which fixes an inkjet print head 24, ink-jet on displacement platform 23
Print head 24 is located at 25 top of substrate.
Ink in storage tank 3 can pass through the inkjet print head 24 in pipeline to forming cavity.Gas-circulating system 4
(Fig. 7) includes a seal cavity 31, is provided with an air inlet 36 at the top of cavity, side is provided with an air outlet 32, inside cavity
It is provided with a drying layer 35, filter layer 34 and circulating fan 33 from top to bottom.
Its working method are as follows: the ink in storage tank 3 is transported in inkjet print head 24, and inkjet print head 24 sprays ink
It shoots out and deposits to 25 surface of substrate, the first layer pattern is printed on substrate 25 by the relative motion of spray head 24 and substrate 25,
The temperature control of substrate 25 solvent boiling point hereinafter, aqueous solvent is made quickly to volatilize, vapor and working gas Ar or N2Mixing
It is removed by being adsorbed after gas-recycling plant 4 by drying layer 35.After ink dried, substrate 25 returns to origin.Using solvent gas
Bulk concentration water finder 5 detects the concentration of vapor in mixed gas, molten using selective laser when its content is in 100ppm
The powder layer material on technique substrate 25 melted is scanned and curing molding is simultaneously connected with substrate 25.Above procedure is repeated to obtain
Obtain multilayer compact block material.In the above process, model of the range 42 of selective laser smelting process scanning in inkjet printing
(Fig. 8) is enclosed within 41.
Using above-mentioned 3D printing device and method thereof, it is fast that SnTe powder suspension prepared by embodiment 4 is used for 3D printing
Speed preparation p-type SnTe thermoelectric arm, includes the following steps:
1) SnTe powder suspension prepared by embodiment 4 is placed in the ink in storage tank as inkjet printing, storage tank
In ink be transported in ink jet printing head under the effect of the pressure；Prepare the Al with a thickness of 1mm2O3Ceramic wafer is in printing base
It is placed on plate and fixed；To molding cavity forvacuum 5 minutes of selective laser melting plant, chamber is then backfilled using Ar gas
Body is to normal pressure, and holding cavity water oxygen content is in 100ppm hereinafter, basal plate preheating to 80 DEG C and keeps the temperature 10 minutes simultaneously；
2) the p-type thermoelectric material powder in storage tank is spread over into Al2O3Ceramic plate surface, then using laser according to setting
The thermo-electric device thermoelectric arm size of meter and distribution are scanned, and are printed as p-type thermoelectric arm and N-shaped thermoelectric arm；Wherein, thermoelectricity is printed
When arm, for powdering with a thickness of 50 microns, laser scan rate is selected as 50mm/s, and laser power is selected as 50W；Repeat the above thermoelectricity
The print procedure of arm is until desired height.
Fig. 4 is p-type SnTe thermoelectric arm laser scanning surface texture after molding, it can be seen that the table after laser melting
Face is very smooth.
The suspension of thermoelectric material can be made in above-described embodiment, due to solid content, the difference of dispersant, suspension
Stability can be variant, but the ink printed thermo-electric device component as ink-jet 3D printing, the stability of example can expire
Foot requires.For solid content, dispersing agent additional amount, the ingredient of powder, the content of solvent and the difference of type, this hair can also be realized
Bright technical solution, embodiment numerous to list herein.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (8)
1. a kind of thermoelectric material powder suspension for 3D printing, it is characterised in that it include thermoelectric material powder, dispersing agent,
Solvent；The solid content of the thermoelectric material powder suspension for 3D printing is calculated as 1 ~ 14.59% with percent by volume, wherein
Dispersing agent is 11.07% ~ 50% relative to thermoelectricity powder percent by volume；The granularity of the thermoelectric material powder at 45 μm hereinafter,
Wherein 1 μm or more of particle fraction cannot be less than 90%, and 10 μm or more of particle fraction cannot be less than 50%.
2. a kind of thermoelectric material powder suspension for 3D printing according to claim 1, it is characterised in that described point
Powder is one of polyvinylpyrrolidone, benzoic acid or polyethylene glycol or several mixtures in any proportion.
3. a kind of thermoelectric material powder suspension for 3D printing according to claim 1, it is characterised in that described molten
Agent is one of water, dehydrated alcohol, acetone or several mixtures in any proportion.
4. a kind of preparation method of thermoelectric material powder suspension for 3D printing described in claim 1, it is characterised in that
Thermoelectric material powder, dispersing agent, solvent are mixed by ball-milling method and suspended to get to the thermoelectric material powder for being used for 3D printing
Liquid.
5. a kind of preparation method of thermoelectric material powder suspension for 3D printing according to claim 4, feature
It is to include the following steps:
1) prepare thermoelectric material powder, dispersing agent, solvent according to the proportion；
2) thermoelectric material powder, dispersing agent and solvent are subjected to ball-milling technology, gained mixed liquor is to be used for 3D printing
Thermoelectric material powder suspension.
6. a kind of preparation method of thermoelectric material powder suspension for 3D printing according to claim 5, feature
It is in step 2 that ball-milling technology is divided into three steps, design parameter are as follows: firstly, setting support plate revolution as 50 ~ 100r/min, grind
Tank revolution is -50 ~ -100r/min, and relative rate is -1, suspends 15 minutes within ball milling 30 minutes, repeats grinding 2 ~ 5 times；Then, it sets
Support plate revolution is 200 ~ 300r/min, and grinding pot revolution is -200 ~ -300r/min, and relative rate is -1, is suspended within ball milling 30 minutes
15 minutes, repeat grinding 6-10 times；Resetting support plate revolution is 50r/min, and grinding pot revolution is -50r/min, relative rate
It is -1, ball milling 30 minutes, suspends 15 minutes, repeat grinding 1 ~ 3 time.
7. a kind of preparation method of thermoelectric material powder suspension for 3D printing according to claim 5, feature
It is to further include the steps that between the step 1) and step 2 by dry, sieving after thermoelectric material powder progress wet-milling.
8. application of the suspension described in claim 1 as 3D printing ink.
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| CN101542763A (en) * | 2006-11-21 | 2009-09-23 | 赢创德固赛有限责任公司 | Thermoelectric elements, method for the production thereof, and use thereof |
| WO2012101457A1 (en) * | 2011-01-28 | 2012-08-02 | Isis Innovation Limited | Exfoliation of layered materials |
| CN105149576A (en) * | 2015-09-18 | 2015-12-16 | 复旦大学 | 3D printing method for rapidly forming thermoelectric materials |
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| CN101542763A (en) * | 2006-11-21 | 2009-09-23 | 赢创德固赛有限责任公司 | Thermoelectric elements, method for the production thereof, and use thereof |
| WO2012101457A1 (en) * | 2011-01-28 | 2012-08-02 | Isis Innovation Limited | Exfoliation of layered materials |
| CN105149576A (en) * | 2015-09-18 | 2015-12-16 | 复旦大学 | 3D printing method for rapidly forming thermoelectric materials |
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