CN106221198A - A kind of 3D printing composite of low warpage - Google Patents
A kind of 3D printing composite of low warpage Download PDFInfo
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- CN106221198A CN106221198A CN201610612797.XA CN201610612797A CN106221198A CN 106221198 A CN106221198 A CN 106221198A CN 201610612797 A CN201610612797 A CN 201610612797A CN 106221198 A CN106221198 A CN 106221198A
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- graphene
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- compounded mix
- low warpage
- sio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
Abstract
The invention discloses the 3D printing composite of a kind of low warpage, it is made up of the raw material of following weight portion meter: nylon 50 ~ 60 parts, PHA5 ~ 10 part, compatilizer 1 ~ 5 part, compound inorganic stuffing 10 ~ 20 parts, coupling agent 1 ~ 2 part, hindered phenol antioxygen 0.1 ~ 0.5 part, phosphite antioxidant 0.5 ~ 1 part, other auxiliary agent 0.1 ~ 0.5 part, wherein, described nylon is 1:(0.1 ~ 0.15 with the weight ratio of PHA), described compound inorganic stuffing is by Graphene/SiO2Compounded mix and graphene/carbon acid calcium compounded mix composition.The 3D printing composite of this low warpage, not only has extremely low contractility, good dimensional stability and good viscosity, is difficult to warp；Also there is the mechanical property of excellence, widened the range of application that 3D prints further.
Description
Technical field
The present invention relates to field of compound material, the 3D printing composite of a kind of low warpage.
Background technology
3D printing technique is also known as a kind of emerging technology of increasing material manufacturing technology, actually rapid shaping field, and it is one
Kind based on mathematical model file, use powdery metal or plastics etc. can jointing material, come by the way of successively printing
The technology of constructed object.Ultimate principle is layered manufacturing, successively increases material and generates the technology of 3D solid.At present, 3D beats
Print technology is applied primarily to product prototype, Making mold and the field such as artistic creation, jewelry-making, substitutes these tradition and depends on
The retrofit technique relied.It addition, 3D printing technique is gradually applied to the necks such as medical science, biological engineering, building, clothing, aviation
Territory, has opened up wide space for innovation.
3D printing technique includes Stereolithography technology, layer separated growth technology, selective laser burning technology and melts
Deposition modeling technology.Selective laser sintering technique is the 3D printing technique being most widely used.Selective Laser Sintering
There is plurality of advantages, as extensive in powder selection, the suitability is wide, manufacturing process is fairly simple, forming accuracy is high, without support knot
Structure, can direct sintering part, therefore paid attention to by the most widely in modern manufacturing industry.But, selective laser sintering
The greatest problem of technique is that the polymeric material being available for sintering is extremely limited, therefore, needs offer one badly and can be applicable to selectivity
The performance preferably composite that laser sintering process uses.And, in print procedure, model be bonded in printer base plate or
During hott bed, owing to nylon crystallization occurs volume contraction to cause printing goods buckling deformation and cause follow-up printing deviation mistake occur
By mistake, even cannot be carried out printing.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides the 3D printing composite of a kind of low warpage,
Not only there is extremely low contractility, good dimensional stability and good viscosity, be difficult to warp；Also there is the mechanics of excellence
Performance, has widened the range of application that 3D prints further.
The technical problem to be solved is achieved by the following technical programs:
A kind of 3D printing composite of low warpage, it is made up of the raw material of following weight portion meter: nylon 50 ~ 60 parts, PHA5 ~
10 parts, compatilizer 1 ~ 5 part, compound inorganic stuffing 10 ~ 20 parts, coupling agent 1 ~ 2 part, hindered phenol antioxygen 0.1 ~ 0.5 part, phosphorous
0.5 ~ 1 part of acid esters antioxidant, other auxiliary agent 0.1 ~ 0.5 part, wherein, described nylon is 1:(0.1 ~ 0.15 with the weight ratio of PHA),
Described compound inorganic stuffing is by Graphene/SiO2Compounded mix and graphene/carbon acid calcium compounded mix composition.
In the present invention, described Graphene/SiO2The weight part ratio of compounded mix and graphene/carbon acid calcium compounded mix is
(1 ~ 3): (1 ~ 2).
In the present invention, described nylon is 1:0.12 with the weight ratio of PHA.
In the present invention, the 3D printing composite of a kind of low warpage, it is made up of the raw material of following weight portion meter: Buddhist nun
Dragon 52 parts, PHA6.24 part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen 0.1 part, phosphorous acid
0.5 part of ester antioxidant, other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 3:2 by weight is by Graphene/SiO2Multiple
Close filler to form with graphene/carbon acid calcium compounded mix.
In the present invention, the 3D printing composite of a kind of low warpage, it is made up of the raw material of following weight portion meter: Buddhist nun
Dragon 60 parts, PHA7.2 part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen 0.1 part, phosphorous acid
0.5 part of ester antioxidant, other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 3:2 by weight is by Graphene/SiO2Multiple
Close filler to form with graphene/carbon acid calcium compounded mix.
In the present invention, described Graphene/SiO2Compounded mix preparation method is as follows: by Graphene 700KW ultrasonic vibration
It is scattered in ethanol under stirring with 1300r/min centrifugal speed；Add 4:1 water and ammonia afterwards, be stirring evenly and then adding into positive silicon
The mass ratio of acetoacetic ester and Graphene is 1.6:1, and regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 4.2 hours, carry out from
The heart also cleans 3 acquisition precipitations with acetone and deionized water, deionized water successively；This is deposited in 90o2h it is dried under C, with
To being coated with SiO2Graphene compounded mix.
In the present invention, the preparation method of described graphene/carbon acid calcium compounded mix is as follows: added by 1 part of Graphene
In 100ml deionized water, after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir, prepare graphite
Alkene dispersion liquid；73 parts of quantum dot calcium carbonate are added in 500ml deionized waters, 1300kW ultrasonic vibration and 1500r/min from
Calcium carbonate dispersion liquid is prepared after the lower dispersion 300min of heart speed stirring；Lower slowly drip in graphene dispersing solution 100kW is ultrasonic
Add calcium carbonate dispersion liquid, ultrasonic 60min, then sucking filtration, drying, prepare graphene/carbon acid calcium compounded mix.
In the present invention, the preparation method of described graphene/carbon acid calcium compounded mix is as follows: added by 1 part of Graphene
In 100ml deionized water, after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir, prepare graphite
Alkene dispersion liquid；73 parts of quantum dot calcium carbonate are added in 500ml deionized waters, 1300kW ultrasonic vibration and 1500r/min from
Calcium carbonate dispersion liquid is prepared after the lower dispersion 300min of heart speed stirring；Lower slowly drip in graphene dispersing solution 100kW is ultrasonic
Add calcium carbonate dispersion liquid, ultrasonic 60min, then sucking filtration, drying, prepare graphene/carbon acid calcium compounded mix.
Other auxiliary agent described is the one or more combination in dispersant, nucleator, lubricant.Described nylon have employed day
The PA12 product of this Ube Industries, Ltd, model is 9048T1, and fusing point is 146 DEG C；Coupling agent have employed excellent generalization in Nanjing
The silane coupler product of work company limited, model is KH560；Hindered phenol antioxygen have employed Ciba of Germany
Irganox 245 product, fusing point is 76～79 DEG C；Phosphite antioxidant have employed the Irgafos 168 of Ciba of Germany
Product, phosphite antioxidant is 1:2 with the use proportioning of hindered phenol antioxygen；It is public that nucleator have employed Brueggemann chemistry
The BRUGGOLEN P22 product of department, and the mixture of powders of inorganic constituents organic for nanoscale.
There is advantages that and obtain scientific matching by test of many times, both realized preferably 3D and printed system
The mechanical property of product, simultaneously the dimensional stability of composite, resistance to warping, all increased substantially, caking property is excellent,
Powder shape comparison rule, even particle size distribution, the property of can be chosen laser sintering and moulding or be prevented effectively from moulded products warpage
Deformation, meets commercial Application to goods precision and the requirement of intensity.
Detailed description of the invention
In the present invention,
(1) Graphene is prepared by following methods: taking a certain amount of acid flat band ink, 1000 DEG C process 2 hours, then 8% in atmosphere
H2Nitrogen and hydrogen mixture in 1100 DEG C of in-situ reducing process 1.0 hours, add macrogol ester and the mass ratio of mass ratio 3%
Tetracarboxylic dianhydride's dinaphthyl of 5.0%, is made into, with water, the slurry that concentration is 82.0%, first enters under the ultrasonic assistant that power is 700W
Row 4000 turns/min ball milling 10 hours, then adjust and to 300W ultrasound wave, carry out 2000 turns/min ball milling 5 hours, through height after ball milling
Speed 10000 turns/min of centrifuge separates, lyophilization, it is thus achieved that Graphene solid.
(2) quantum dot calcium carbonate, its preparation method refers to a kind of microemulsion disclosed in Chinese patent CN103570051B
System prepares the method for nano calcium carbonate quantum dot, the most first prepares the nano-calcium carbonate microemulsion of 1 ~ 3nm, more rotated
Evaporate and be dried and prepare quantum dot calcium carbonate powder.
(3) Graphene/SiO2Compounded mix preparation method is as follows: by Graphene ultrasonic agitation (700KW ultrasonic vibration and
1300r/min centrifugal speed stirs) it is scattered in ethanol；Add a certain proportion of (4:1) water and ammonia afterwards, after stirring
The mass ratio adding tetraethyl orthosilicate and Graphene is 1.6:1, and regulation pH value is 9, and reaction temperature is 25 DEG C, and reaction 4.2 is little
Time, it is centrifuged and cleans 3 times with acetone and deionized water, deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 2h, to obtain being coated with SiO2Graphene compounded mix.
(4) preparation method of graphene/carbon acid calcium compounded mix is as follows: 1 part of Graphene is added 100ml deionized water
In, prepare graphene dispersing solution after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir；By 73
Part quantum dot calcium carbonate adds in 500ml deionized water, divides under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir
Calcium carbonate dispersion liquid is prepared after dissipating 300min；Lower in graphene dispersing solution, it is slowly added dropwise calcium carbonate dispersion liquid 100kW is ultrasonic,
Ultrasonic 60min, then sucking filtration, drying, prepare graphene/carbon acid calcium compounded mix.
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1 ~ 5, comparative example 1 ~ 3, concrete formula is shown in Table 1.
Embodiment 1
The 3D printing composite of a kind of low warpage, it is made up of the raw material of following weight portion meter: nylon 52 parts, PHA6.24
Part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen 0.1 part, phosphite antioxidant 0.5 part,
Other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 1:3 by weight is by Graphene/SiO2Compounded mix and Graphene/
Calcium Carbonate Composite Fillers forms.
The preparation method of the 3D printing composite of a kind of low warpage is as follows:
(1) nylon of half and compound inorganic stuffing are added in banbury in 280 degrees Celsius of lower melt blendings, prepare nylon/
Filler master batch；
(2) second half nylon, PHA and compatilizer are added in banbury in 280 degrees Celsius of lower melt blendings, prepare nylon/
PHA master batch；
(3) nylon/filler master batch, nylon/PHA master batch, remaining component and trifluoroethanol are put in nitrogen charging hermetic container, three
Fluoroethanol solvent load is nylon resin quality: the mass volume ratio of trifluoroethanol solvent is 1:2g/mL, is stirred continuously, and is formed
Nylon lysate；
(4) by peristaltic pump, lysate is transported in spray dryer, carries out under nitrogen protection being atomized, be dried, powder is received
Collection and formic acid recycling；Intake air temperature is 130 ± 2 DEG C, and air outlet temperature is 90 ± 2 DEG C, oxygen concentration≤1.5%；
The powder of collection is placed in vacuum drier, normal temperature drying 3 hours, packs, obtain 3D and print by low warpage compound
Material.
Embodiment 2
Based on embodiment 1, difference is: described compound inorganic stuffing 3:2 by weight is by Graphene/SiO2It is combined and fills out
Material forms with graphene/carbon acid calcium compounded mix.
Embodiment 3
Based on embodiment 1, difference is: described compound inorganic stuffing 4:1 by weight is by Graphene/SiO2It is combined and fills out
Material forms with graphene/carbon acid calcium compounded mix.
Embodiment 4
Based on embodiment 1, difference is: the 3D printing composite of a kind of low warpage, it is by following weight portion meter
Raw material forms: nylon 60 parts, PHA7.2 part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen 0.1
Part, phosphite antioxidant 0.5 part, other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 3:2 by weight is by graphite
Alkene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix.
Embodiment 5
Based on embodiment 1, difference is: the 3D printing composite of a kind of low warpage, it is by following weight portion meter
Raw material forms: nylon 50 parts, PHA5 part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen 0.1
Part, phosphite antioxidant 0.5 part, other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 3:2 by weight is by graphite
Alkene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix.
Embodiment 6
Based on embodiment 1, difference is: the 3D printing composite of a kind of low warpage, it is by following weight portion meter
Raw material forms: nylon 60 parts, PHA9 part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen 0.1
Part, phosphite antioxidant 0.5 part, other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 3:2 by weight is by graphite
Alkene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix.
Comparative example 1
Based on embodiment 1, difference is: the 3D printing composite of a kind of low warpage, it is by following weight portion meter
Raw material forms: nylon 52 parts, PHA6.24 part, 2 parts, 6 parts SiO of compatilizer2, 6 parts of calcium carbonate, coupling agent 1, hindered phenol antioxygens
0.1 part, phosphite antioxidant 0.5 part, other auxiliary agent 0.5 part.
Comparative example 2
Based on embodiment 1, difference is: the 3D printing composite of a kind of low warpage, it is by following weight portion meter
Raw material forms: nylon 52 parts, PHA6.24 part, 2 parts, 5 parts SiO of compatilizer2, 5 parts of calcium carbonate, 1 part of Graphene, coupling agent 1, be subject to
Resistance 0.1 part of phenol antioxidant, phosphite antioxidant 0.5 part, other auxiliary agent 0.5 part.
Comparative example 3
Based on embodiment 1, difference is: the 3D printing composite of a kind of low warpage, it is by following weight portion meter
Raw material forms: nylon 52 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen 0.1 part, phosphite antioxidant
0.5 part, other auxiliary agent 0.5 part, wherein, described compound inorganic stuffing 3:2 by weight is by Graphene/SiO2Compounded mix with
Graphene/carbon acid calcium compounded mix forms.
Performance evaluation mode and the standard of implementation: the composite prepared by said method is placed in 3D printer (Germany EOS
The P396 EOSINT powder sintered system of P396 laser plastic) in, and printing standard specimen according to GB, paving powder thickness is
0.12mm, preheating temperature is 174 DEG C, and laser power is 70w, and scanning speed is 4 ms/h.
The stretching yield stress of sample, tensile strain at yield, elongation at break, Izod notched impact is detected according to GB
Intensity and shrinkage factor test.Test result is as follows:
As can be seen here, 3D printing composite of the present invention has good molding processibility, and compared with comparative example, size
Stability, resistance to warping, stretching yield stress, IZOD notch impact strength are all increased substantially, particularly embodiment
2, the product of 4, through test of many times, scientific compatibility obtains optimal effect.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained
Art scheme, all should fall within the scope and spirit of the invention.
Claims (7)
1. a 3D printing composite for low warpage, it is made up of the raw material of following weight portion meter: nylon 50 ~ 60 parts,
PHA5 ~ 10 part, compatilizer 1 ~ 5 part, compound inorganic stuffing 10 ~ 20 parts, coupling agent 1 ~ 2 part, hindered phenol antioxygen 0.1 ~ 0.5 part,
Phosphite antioxidant 0.5 ~ 1 part, other auxiliary agent 0.1 ~ 0.5 part, wherein, the weight ratio of described nylon and PHA be 1:(0.1 ~
0.15), described compound inorganic stuffing is by Graphene/SiO2Compounded mix and graphene/carbon acid calcium compounded mix composition.
The 3D printing composite of low warpage the most according to claim 1, it is characterised in that described Graphene/SiO2Multiple
The weight part ratio closing filler and graphene/carbon acid calcium compounded mix is (1 ~ 3): (1 ~ 2).
The 3D printing composite of low warpage the most according to claim 1, it is characterised in that described nylon is with PHA's
Weight ratio is 1:0.12.
The 3D printing composite of low warpage the most according to claim 1, it is characterised in that it is by following weight portion meter
Raw material composition: nylon 52 parts, PHA6.24 part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen
0.1 part, phosphite antioxidant 0.5 part, other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 3:2 by weight is by stone
Ink alkene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix.
The 3D printing composite of low warpage the most according to claim 1, it is characterised in that it is by following weight portion meter
Raw material composition: nylon 60 parts, PHA7.2 part, compatilizer 2 parts, compound inorganic stuffing 12 parts, coupling agent 1, hindered phenol antioxygen
0.1 part, phosphite antioxidant 0.5 part, other auxiliary agent 0.5 part；Wherein, described compound inorganic stuffing 3:2 by weight is by stone
Ink alkene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix.
6. according to the 3D printing composite of the arbitrary described low warpage of claim 1 to 5, it is characterised in that described graphite
Alkene/SiO2Compounded mix preparation method is as follows: Graphene 700KW ultrasonic vibration and 1300r/min centrifugal speed are stirred lower point
Dissipate in ethanol；Adding 4:1 water and ammonia afterwards, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is
1.6:1, regulation pH value is 9, and reaction temperature is 25 DEG C, react 4.2 hours, be centrifuged and use successively acetone and deionized water,
Deionized water cleans 3 times and obtains precipitation；This is deposited in 90o2h it is dried, to obtain being coated with SiO under C2Graphene compound fill out
Material.
7. according to the 3D printing composite of the arbitrary described low warpage of claim 1 to 5, it is characterised in that described graphite
The preparation method of alkene/Calcium Carbonate Composite Fillers is as follows: added by 1 part of Graphene in 100ml deionized water, in the ultrasonic shake of 800kW
Graphene dispersing solution is prepared after the lower dispersion 200min of dynamic and 1300r/min centrifugal speed stirring；73 parts of quantum dot calcium carbonate are added
Enter in 500ml deionized water, after disperseing 300min under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir, prepare carbon
Acid calcium dispersion liquid；Lower in graphene dispersing solution, it is slowly added dropwise calcium carbonate dispersion liquid, ultrasonic 60min 100kW is ultrasonic, then takes out
Filter, drying, prepare graphene/carbon acid calcium compounded mix.
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| CN201610612797.XA CN106221198A (en) | 2016-07-29 | 2016-07-29 | A kind of 3D printing composite of low warpage |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135265A (en) * | 2018-07-24 | 2019-01-04 | 常州达奥新材料科技有限公司 | Carrier-free heat resistanceheat resistant oxygen solution type nylon bloom modified master |
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| CN104910614A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | Low-warpage nylon powder composite material for 3D printing and preparation method thereof |
| CN105419309A (en) * | 2015-12-18 | 2016-03-23 | 黄志华 | Preparation method of luminescent polyamide composite material |
| CN105778484A (en) * | 2016-03-15 | 2016-07-20 | 东华大学 | Modified nylon material for 3D printing applied to FDM (fused deposition molding) technology and printing method of modified nylon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194296A (en) * | 2014-09-19 | 2014-12-10 | 叶川 | High-strength degradable 3D printing material and preparation method thereof |
| CN104910614A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | Low-warpage nylon powder composite material for 3D printing and preparation method thereof |
| CN105419309A (en) * | 2015-12-18 | 2016-03-23 | 黄志华 | Preparation method of luminescent polyamide composite material |
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| CN109135265A (en) * | 2018-07-24 | 2019-01-04 | 常州达奥新材料科技有限公司 | Carrier-free heat resistanceheat resistant oxygen solution type nylon bloom modified master |
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Application publication date: 20161214 |