CN104845300A - Polylactic acid composite material used for three-dimensional printing and preparation method therefor - Google Patents
Polylactic acid composite material used for three-dimensional printing and preparation method therefor Download PDFInfo
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Abstract
The invention discloses a polylactic acid composite material used for three-dimensional printing. The polylactic acid composite material is characterized by comprising sheet-like micro metal powder, and being prepared from raw materials of the following components in parts by weight: 70-80 parts of polylactic acid, 5-15 parts of sheet-like micro metal powder, 1-2 parts of a surface modifier, 0.5-1 part of a crystallizing agent, 0.2-0.3 part of an antioxidant and 0.2-0.3 part of a processing aid. The sheet-like micro metal powder with flexibility and good thermal capacity is introduced into the polylactic acid, so that the thermal performance of the polylactic acid is changed by utilizing the thermal capacity of the sheet-like micro metal powder, and the polylactic acid is prevented from being quickly cooled to generate deformation. Especially, the sheet-like metal powder has good sliding property and flexibility, so that the flow uniformity and the toughness of the polylactic acid are improved, and the polylactic acid composite material is suitable for manufacturing a high-precision product by three-dimensional printing.
Description
Technical field
The invention belongs to 3D and print manufacture field, be specifically related to a kind of lactic acid composite material manufactured for 3 D-printing, and relate to the preparation method of this lactic acid composite material further.
Background technology
3D printing technique a kind ofly piles up material generate the quick increasing material manufacturing technology of 3D solid by successively increasing, and not only overcomes tradition and subtract the loss that material manufacture causes, and make product manufacturing more intelligent, more precisely, more efficiently.3D prints the new trend that manufacturing technology represents world's development of manufacturing, for the development of quickening advanced manufacturing industry, promotes that industrial repositioning upgrading has important leading action.Along with high-end manufacturing development, current 3D prints manufacturing technology and is shown great attention to, and is called as the gordian technique promoting the third time Industrial Revolution together with robot technology, artificial intelligence technology.
Because 3D prints molding mode and principle that manufacturing technology changes product completely, be overturning traditional manufacturing mode, therefore material bottleneck becomes the problem that restriction 3D prints development, is also key point and the difficult point place that 3D prints breakthrough and innovation.At present, material conventional in 3D printing technique is thermoplastic polymer, the melted extrusion modeling forming technique (FDM) printed by 3D, utilize thermoplastic, polymeric materials in the molten state, squeeze out from shower nozzle, solidify the thin layer forming outline shape, pile up formation product by being layering of thin layer.Melted extrusion modeling molded polymer material conventional at present has acrylonitrile-butadiene-styrene terpolymer (ABS), poly(lactic acid) (PLA), nylon (PA) etc.
Due to the good thermal fluidity of polymer materials, cool cementability, higher physical strength fast, print manufacture field at 3D and obtain application and development fast.Especially poly(lactic acid) have nontoxic, without the characteristic of pungent smell, in 3D printed material, obtain good application.But the key due to fused glass pellet technique keeps half mobility of material, even solidification shaping, and poly(lactic acid) is a kind of crystalline structure, directly from solid to liquid conversion during heating, temperature reduces then rapid solidification, therefore during cooling, nozzle phase change is large, easy plug nozzle, there is buckling deformations in the product of formation.Especially the crystallographic rigidity of poly(lactic acid), cause poly(lactic acid) easily to be broken as lacking toughness during 3D printing consumables, cannot long-time stable shaping, cause printing to have some setbacks, shaping product lacking toughness and intensity, the product that poly(lactic acid) is printed is very restricted in precision, intensity.
China Patent Publication No. CN103146164A discloses a kind of poly-lactic acid material nano material toughened for rapid shaping and preparation method thereof, and the method utilizes twin screw extruder to carry out blending extrusion toughening modifying to polyacrylic acid ester microsphere and poly(lactic acid).
China Patent Publication No. CN103087489A discloses a kind of modified polylactic acid material and preparation method thereof, the method polyether polyamide elastomer and polynite are as properties-correcting agent, do modified device with twin screw extruder, enhance tensile strength and the toughness of poly(lactic acid).
China Patent Publication No. CN102134381A discloses a kind of modified polylactic acid material and preparation method thereof, in the method, toughness reinforcing heat-resistant elastomer properties-correcting agent and polylactic acid blend are extruded modification, namely improve the defect of the poor toughness of poly(lactic acid), also improve the heat resisting temperature of poly(lactic acid).
When 3D printing melted extrusion modeling is shaping, require that material has good thermal transition performance, namely can become half flowable state during heating, be beneficial to evenly shaping, even solidification during cooling, prevent thermal contraction to be out of shape.According to above-mentioned, blending and modifying at present to poly(lactic acid), by increasing toughening material, its toughness is improved, but thermal transition characteristic does not obviously change, because poly(lactic acid) has definite melting point during heating, directly from solid to liquid conversion, easily trickle time successively shaping, temperature reduces then rapid solidification, and therefore thermal contraction distortion is large, is difficult to print high precision goods.
Summary of the invention
Because of having crystallinity definite melting point when current poly(lactic acid) is used for 3D printing consumables, easily trickle when melted extrusion modeling is shaping, temperature reduces then rapid solidification, and cause 3D to print difficulty, thermal contraction distortion is large, is difficult to printing high precision goods.For this defect, the present invention proposes a kind of lactic acid composite material for 3 D-printing.By introducing sheet micro-fine metal powder in poly(lactic acid), utilizing the thermal capacitance of sheet micro-fine metal powder thus the thermal characteristics of change poly(lactic acid), is semi-fluid when making poly(lactic acid) melted extrusion modeling shaping, prevent trickling, solidify when shaping cooling evenly, thermal contraction diminishes, and prevents from warping; Further, sheet micro-fine metal powder has good sliding and snappiness, promotes poly(lactic acid) Uniform Flow when 3 D-printing, is adapted to print high precision goods.
Further, a kind of preparation method of the lactic acid composite material for 3 D-printing is provided.
For a lactic acid composite material for 3 D-printing, be achieved by the following technical solution:
For a lactic acid composite material for 3 D-printing, it is characterized in that: containing sheet micro-fine metal powder, be prepared from by the raw material of following component by weight:
Poly(lactic acid) 70-80 part,
Sheet micro-fine metal powder 5-15 part,
Coating materials 1-2 part,
Crystallizing agent 0.5-1 part,
Oxidation inhibitor 0.2-0.3 part,
Processing aid 0.2-0.3 part,
Described poly(lactic acid) is number-average molecular weight 10-15 ten thousand, the powder poly(lactic acid) of being sieved by 50 orders, and under the test condition of 190 DEG C × 2.16kg, melting index is 4-6g/10min;
Described sheet micro-fine metal powder is median size 10-20 μm, and radius-thickness ratio is greater than at least one in the fine flake aluminum of 20, fine zinc flake, fine flake iron powder, fine sheet Stainless Steel Powder, fine Nickel Powder, fine sheet titanium valve, fine flake copper, fine sheet zinc aluminium alloy powder;
Described coating materials is at least one in stearic acid sorbitan ester, single palmitinic acid sorbitan ester, sorbitan monooleate, polyoxyethylene sorbitan monooleate;
Described crystallizing agent is polyethylene oxide;
Described oxidation inhibitor is hindered phenol type antioxidant four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester compositely to form by weight 1: 1;
Described processing aid is at least one in N, N '-bis-ethylene hard fatty acids acid amides, stearic amide, paraffin, polyethylene wax, Poly Propylene Wax.
The preparation method of a kind of lactic acid composite material for 3 D-printing of the present invention, is characterized in that carrying out in the following manner:
1) the sheet micro-fine metal powder of 5-15 weight part, the coating materials of 1-2 weight part are joined in pulverizing mill, setting pulverizing mill temperature 80-100 DEG C, with 1200-1500rpm speed high speed dispersion 5-10min, sheet fine metal powder boundling is dispersed throughout, then the oxidation inhibitor adding 0.2-0.3 weight part continues dispersion 3-5min, obtains tool activated sheet fine metal powder;
2) crystallizing agent of active sheet fine metal powder step 1) obtained and the polylactic acid powder of 70-80 weight part, 0.5-1 weight part adds high-speed mixer, under 40-50 DEG C of condition, with the rotating speed mixing 10-20min of 300-900rpm, then the processing aid dispersing and mixing 3-5min of 0.2-0.3 weight part is added, blowing after the complete melting dispersion of processing aid;
3) by step 2) material that obtains is placed in screw extruder, extrude under 140-175 DEG C of condition, the single hole mould being 3mm by aperture forms circular bar, through the thermostat container constant temperature back draft of 70-80 DEG C, batches and obtains the even thread lactic acid composite material of diameter at about 1.75mm.
Above-mentioned preparation method the 1st) pulverizing mill described in step is vertical air-flow pulverizing mill, be made up of stationary knife and moving knife, the moving knife of high speed rotating forms high velocity air, under the impact that high velocity air is formed, sheet fine metal powder is fluidization, each fine powder is made to have single kinestate, realize disperseing also and coating materials activation modification sheet fine metal powder boundling, thus form activating sheet micro-fine metal powder, sheet activated fine metal powder has higher radius-thickness ratio, two-dimension plane structure, not only sliding capability is excellent, and there is good snappiness and thermal capacitance.
Above-mentioned preparation method the 2nd) high-speed mixer described in step adopts the high-speed mixer of the models such as currently reported and/or that use SHR-200A, SHR-300A, SHR-500A, has good mixing dispersion effect under the agitation condition of 300-900rpm.
Above-mentioned preparation method the 3rd) screw extruder described in step is parallel dual-screw extruding machine, by the shearing of rotating in same direction screw rod, makes flake metal powder be dispersed in poly(lactic acid), wherein more preferably parallel dual-screw extruding machine length-to-diameter ratio at 20-25
:1, be provided with vacuum volatilization device, make material in once producing, just can complete batch mixing, mixing, plasticizing, shear disperse, the whole process of homogenizing and dehydration, melt residence time in machine barrel is short, decreases the thermal destruction of poly(lactic acid).On this basis, the further span of control of its main operating parameters is: engine speed 150-300 rev/min, feeding machine rotating speed 8-30 rev/min; Extrusion temperature span of control: one to three district 140-145 DEG C, four to six district 169-175 DEG C, seven to ten district 140-145 DEG C.
Above-mentioned preparation method the 3rd) thermostat container described in step adopts hot blast constant temperature, avoid the deformation that water-cooled causes, under 70-80 DEG C of condition, lactic acid composite material has good visco-elasticity, can carry out uniform and stable stretching, the thread lactic acid composite material circularity obtained is controlled within positive and negative 0.02mm.
A kind of lactic acid composite material for 3 D-printing of the present invention, by introducing the sheet micro-fine metal powder with flexible and good thermal capacitance in poly(lactic acid), utilize the thermal capacitance of sheet micro-fine metal powder thus the thermal characteristics of change poly(lactic acid), when 3 D-printing preheating, sheet micro-fine metal powder stores amount of heat, when poly(lactic acid) is shaping by three-dimensional melted extrusion modeling flake metal powder progressively heat release make poly(lactic acid) formed semi-fluid, prevent trickling, the flake metal powder heat absorption when shaping cooling, and make poly(lactic acid) be in viscoelastic state, prevent poly(lactic acid) from cooling generation deformation fast.Especially flake metal powder has good sliding, is dispersed in poly(lactic acid) and promotes poly(lactic acid) uniform flow when the melting nozzle by 3 D-printing; Sheet micro-fine metal powder has snappiness, and the toughness of poly(lactic acid) is improved.Therefore, the present invention is adapted to print high precision goods for the lactic acid composite material of 3 D-printing.
The preparation method of a kind of lactic acid composite material for 3 D-printing of the present invention, by the high velocity air that pulverizing mill is formed, each fine powder is made to have single kinestate, realize disperseing also and coating materials activation modification fine metal sheet powder boundling, thus form activated fine tinsel, make to have higher radius-thickness ratio, the fine metal sheet of two-dimension plane structure is dispersed in poly(lactic acid), not only sliding capability is excellent, and has good snappiness and thermal capacitance.Adopted by hot blast constant temperature, avoid the deformation that water-cooled causes, under 70-80 DEG C of condition, lactic acid composite material has good visco-elasticity, can carry out uniform and stable stretching, and the thread poly(lactic acid) composite filament circularity obtained is controlled within positive and negative 0.02mm.
A kind of lactic acid composite material for 3 D-printing of the present invention and preparation method thereof, compared with prior art, its outstanding feature and excellent effect are:
1, a kind of lactic acid composite material for 3 D-printing of the present invention, containing having high heat capacity and flexible flake metal powder, change the thermal characteristics of poly(lactic acid), when this lactic acid composite material carries out melt extruded 3 D-printing, the flake metal powder contained progressively heat release makes poly(lactic acid) form semi-fluid, prevents trickling, the flake metal powder heat absorption when shaping cooling, and make poly(lactic acid) be in viscoelastic state, prevent poly(lactic acid) from cooling generation deformation fast.
2, a kind of lactic acid composite material for 3 D-printing of the present invention, has good sliding containing flake metal powder, promotes poly(lactic acid) uniform flow when the melting nozzle by 3 D-printing; Sheet micro-fine metal powder has snappiness, and the toughness of poly(lactic acid) is improved.This lactic acid composite material is adapted to 3 D-printing high precision goods.
3, the preparation method of a kind of lactic acid composite material for 3 D-printing of the present invention, by the high velocity air that pulverizing mill is formed, each fine powder is made to have single kinestate, realize disperseing also and coating materials activation modification fine metal sheet powder boundling, thus form activated fine tinsel, make to have higher radius-thickness ratio, the fine metal sheet of two-dimension plane structure is dispersed in poly(lactic acid), not only sliding capability is excellent, and has good snappiness and thermal capacitance.
4, the preparation method of a kind of lactic acid composite material for 3 D-printing of the present invention, adopted by hot blast constant temperature, avoid the deformation that water-cooled causes, under 70-80 DEG C of condition, lactic acid composite material has good visco-elasticity, can carry out uniform and stable stretching, the poly(lactic acid) composite filament circularity obtained is controlled within positive and negative 0.02mm.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
embodiment 1
1) by the fine flake aluminum of 5 weight parts, the coating materials stearic acid sorbitan ester of 2 weight parts joins in pulverizing mill, setting pulverizing mill temperature 80 DEG C, with 1200rpm speed high speed dispersion 5min, sheet fine metal powder boundling is dispersed throughout, then 0.2 weight part is added by hindered phenol type antioxidant four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester is by weight 1: 1 composite oxidation inhibitor, continue dispersion 3-5min, obtain tool activated sheet fine metal powder,
2) polyethylene oxide of active sheet fine metal powder step 1) obtained and the polylactic acid powder of 70 weight parts, 0.5 weight part adds high-speed mixer, under 40 DEG C of conditions, with the rotating speed mixing 10min of 300rpm, then the Poly Propylene Wax dispersing and mixing 5min of 0.2 weight part is added, blowing after the complete melting dispersion of processing aid;
3) by step 2) material that obtains is placed in length-to-diameter ratio 25
:the parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material in once producing, just can complete batch mixing, mixing, plasticizing, shear disperse, the whole process of homogenizing and dehydration, on this basis, engine speed 150 revs/min, feeding machine rotating speed 8 revs/min; Extrusion temperature span of control: one to three district 140-145 DEG C, four to six district 169-175 DEG C, seven to ten district 140-145 DEG C, the single hole mould being 3mm by aperture forms circular bar, through the thermostat container constant temperature back draft of 70-80 DEG C, batches and obtains the even thread lactic acid composite material of diameter at about 1.75mm.
Thread lactic acid composite material performance data embodiment 1 obtained is as following table:
| Interventions Requested | Detected result |
| Mean diameter (mm) | 1.75 |
| Diameter tolerance (mm) | ±0.02 |
| Tensile strength (MPa) | 2.82 |
| Melt temperature | 175℃ |
| Solution flow index (g/10min) | 8 |
| Condensing temperature (DEG C) | 80 DEG C of uniform and stable condensations |
Thread lactic acid composite material embodiment 1 obtained is sent into hot melt nozzle and is carried out 3 D-printing, half flowable state is become under 175 DEG C of conditions, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and error in design, within ± 0.1mm, are adapted to printing high precision goods.
embodiment 2
1) by the fine zinc flake of 10 weight parts, the coating materials list palmitinic acid sorbitan ester of 1.5 weight parts joins in pulverizing mill, setting pulverizing mill temperature 85 DEG C, with 1500rpm speed high speed dispersion 10min, sheet fine metal powder boundling is dispersed throughout, then 0.2 weight part is added by hindered phenol type antioxidant four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester is by weight 1: 1 composite oxidation inhibitor, continue dispersion 4min, obtain tool activated sheet fine metal powder,
2) the crystallizing agent polyethylene oxide of active sheet fine metal powder step 1) obtained and the polylactic acid powder of 75 weight parts, 1 weight part adds high-speed mixer, under 45 DEG C of conditions, with the rotating speed mixing 15min of 500rpm, then the processing aid polyethylene wax dispersing and mixing 5min of 0.3 weight part is added, blowing after the complete melting dispersion of processing aid;
3) by step 2) material that obtains is placed in length-to-diameter ratio 20
:the parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material in once producing, just can complete batch mixing, mixing, plasticizing, shear disperse, the whole process of homogenizing and dehydration, on this basis, engine speed 200 revs/min, feeding machine rotating speed 10 revs/min; Extrusion temperature span of control: one to three district 140-145 DEG C, four to six district 169-175 DEG C, seven to ten district 140-145 DEG C, the single hole mould being 3mm by aperture forms circular bar, through the thermostat container constant temperature back draft of 70-80 DEG C, batches and obtains the even thread lactic acid composite material of diameter at about 1.74mm.
Thread lactic acid composite material performance data embodiment 2 obtained is as following table:
| Interventions Requested | Detected result |
| Mean diameter (mm) | 1.74 |
| Diameter tolerance (mm) | ±0.02 |
| Tensile strength (MPa) | 2.66 |
| Melt temperature | 175℃ |
| Solution flow index (g/10min) | 8．6 |
| Condensing temperature (DEG C) | 75 DEG C of uniform and stable condensations |
Thread lactic acid composite material embodiment 2 obtained is sent into hot melt nozzle and is carried out 3 D-printing, half flowable state is become under 175 DEG C of conditions, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and error in design, within ± 0.1mm, are adapted to printing high precision goods.
embodiment 3
1) by the fine sheet zinc aluminium alloy powder of 15 weight parts, the coating materials sorbitan monooleate of 2 weight parts joins in pulverizing mill, setting pulverizing mill temperature 100 DEG C, with 1300rpm speed high speed dispersion 10min, sheet fine metal powder boundling is dispersed throughout, then 0.3 weight part is added by hindered phenol type antioxidant four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester continues dispersion 3min by weight 1: 1 composite oxidation inhibitor, obtain tool activated sheet fine metal powder,
2) the crystallizing agent polyethylene oxide of active sheet fine metal powder step 1) obtained and the polylactic acid powder of 80 weight parts, 0.5 weight part adds high-speed mixer, under 50 DEG C of conditions, with the rotating speed mixing 20min of 900rpm, then the processing aid N of 0.2 weight part is added, N '-bis-ethylene hard fatty acids acid amides dispersing and mixing 5min, blowing after the complete melting dispersion of processing aid;
3) by step 2) material that obtains is placed in length-to-diameter ratio 25
:the parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material in once producing, just can complete batch mixing, mixing, plasticizing, shear disperse, the whole process of homogenizing and dehydration, on this basis, engine speed 300 revs/min, feeding machine rotating speed 25 revs/min; Extrusion temperature span of control: one to three district 140-145 DEG C, four to six district 169-175 DEG C, seven to ten district 140-145 DEG C, the single hole mould being 3mm by aperture forms circular bar, through the thermostat container constant temperature back draft of 70-80 DEG C, batches and obtains the even thread lactic acid composite material of diameter at about 1.75mm.
Thread lactic acid composite material embodiment 3 obtained is sent into hot melt nozzle and is carried out 3 D-printing, half flowable state is become under 175 DEG C of conditions, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and error in design, within ± 0.1mm, are adapted to printing high precision goods.
embodiment 4
1) by the fine flake iron powder of 15 weight parts, the coating materials polyoxyethylene sorbitan monooleate of 2 weight parts joins in pulverizing mill, setting pulverizing mill temperature 90 DEG C, with 1200rpm speed high speed dispersion 10min, sheet fine metal powder boundling is dispersed throughout, then 0.3 weight part is added by hindered phenol type antioxidant four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester continues dispersion 3min by weight 1: 1 composite oxidation inhibitor, obtain tool activated sheet fine metal powder,
2) the crystallizing agent polyethylene oxide of active sheet fine metal powder step 1) obtained and the polylactic acid powder of 70 weight parts, 0.5 weight part adds high-speed mixer, under 50 DEG C of conditions, with the rotating speed mixing 10min of 400rpm, then the processing aid stearic amide dispersing and mixing 3min of 0.2 weight part is added, blowing after the complete melting dispersion of processing aid;
3) by step 2) material that obtains is placed in length-to-diameter ratio 20
:the parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material in once producing, just can complete batch mixing, mixing, plasticizing, shear disperse, the whole process of homogenizing and dehydration, on this basis, engine speed 220 revs/min, feeding machine rotating speed 15 revs/min; Extrusion temperature span of control: one to three district 140-145 DEG C, four to six district 169-175 DEG C, seven to ten district 140-145 DEG C, the single hole mould being 3mm by aperture forms circular bar, through the thermostat container constant temperature back draft of 70-80 DEG C, batches and obtains the even thread lactic acid composite material of diameter at about 1.75mm.
Thread lactic acid composite material embodiment 4 obtained is sent into hot melt nozzle and is carried out 3 D-printing, half flowable state is become under 175 DEG C of conditions, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and error in design, within ± 0.1mm, are adapted to printing high precision goods.
embodiment 5
1) by the fine Nickel Powder of 10 weight parts, the coating materials sorbitan monooleate of 1 weight part joins in pulverizing mill, setting pulverizing mill temperature 100 DEG C, with 1300rpm speed high speed dispersion 10min, sheet fine metal powder boundling is dispersed throughout, then 0.3 weight part is added by hindered phenol type antioxidant four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester continues dispersion 3min by weight 1: 1 composite oxidation inhibitor, obtain tool activated sheet fine metal powder,
2) the crystallizing agent polyethylene oxide of active sheet fine metal powder step 1) obtained and the polylactic acid powder of 80 weight parts, 0.5 weight part adds high-speed mixer, under 50 DEG C of conditions, with the rotating speed mixing 20min of 900rpm, then the processing aid N of 0.2 weight part is added, N '-bis-ethylene hard fatty acids acid amides dispersing and mixing 5min, blowing after the complete melting dispersion of processing aid;
3) by step 2) material that obtains is placed in length-to-diameter ratio 25
:the parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material in once producing, just can complete batch mixing, mixing, plasticizing, shear disperse, the whole process of homogenizing and dehydration, on this basis, engine speed 300 revs/min, feeding machine rotating speed 25 revs/min; Extrusion temperature span of control: one to three district 140-145 DEG C, four to six district 169-175 DEG C, seven to ten district 140-145 DEG C, the single hole mould being 3mm by aperture forms circular bar, through the thermostat container constant temperature back draft of 70-80 DEG C, batches and obtains the even thread lactic acid composite material of diameter at about 1.75mm.
Thread lactic acid composite material embodiment 5 obtained is sent into hot melt nozzle and is carried out 3 D-printing, half flowable state is become under 175 DEG C of conditions, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and error in design, within ± 0.1mm, are adapted to printing high precision goods.
Claims (5)
1. for a lactic acid composite material for 3 D-printing, it is characterized in that: containing sheet micro-fine metal powder, the raw material by weight primarily of following component forms:
Poly(lactic acid) 70-80 part,
Sheet micro-fine metal powder 5-15 part,
Coating materials 1-2 part,
Crystallizing agent 0.5-1 part,
Oxidation inhibitor 0.2-0.3 part,
Processing aid 0.2-0.3 part,
Described poly(lactic acid) is number-average molecular weight 10-15 ten thousand, the powder poly(lactic acid) of being sieved by 50 orders, and under the test condition of 190 DEG C × 2.16kg, melting index is 4-6g/10min;
Described sheet micro-fine metal powder is median size 10-20 μm, and radius-thickness ratio is greater than at least one in the fine flake aluminum of 20, fine zinc flake, fine flake iron powder, fine sheet Stainless Steel Powder, fine Nickel Powder, fine sheet titanium valve, fine flake copper, fine sheet zinc aluminium alloy powder;
Described coating materials is at least one in stearic acid sorbitan ester, single palmitinic acid sorbitan ester, sorbitan monooleate, polyoxyethylene sorbitan monooleate;
Described crystallizing agent is polyethylene oxide;
Described oxidation inhibitor is hindered phenol type antioxidant four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester compositely to form by weight 1: 1;
Described processing aid is at least one in N, N '-bis-ethylene hard fatty acids acid amides, stearic amide, paraffin, polyethylene wax, Poly Propylene Wax.
2. prepare as claimed in claim 1 for a method for the lactic acid composite material of 3 D-printing, it is characterized in that the raw material of weight ratio according to claim 1 to process as follows:
1) the sheet micro-fine metal powder of 5-15 weight part, the coating materials of 1-2 weight part are joined in pulverizing mill, setting pulverizing mill temperature 80-100 DEG C, with 1200-1500rpm speed high speed dispersion 5-10min, sheet fine metal powder boundling is dispersed throughout, then the oxidation inhibitor adding 0.2-0.3 weight part continues dispersion 3-5min, obtains tool activated sheet fine metal powder;
2) crystallizing agent of active sheet fine metal powder step 1) obtained and the polylactic acid powder of 70-80 weight part, 0.5-1 weight part adds high-speed mixer, under 40-50 DEG C of condition, with the rotating speed mixing 10-20min of 300-900rpm, then the processing aid dispersing and mixing 3-5min of 0.2-0.3 weight part is added, blowing after the complete melting dispersion of processing aid;
3) by step 2) material that obtains is placed in screw extruder, extrude under 140-175 DEG C of condition, the single hole mould being 3mm by aperture forms circular bar, screw extruder is provided with vacuum volatilization device, make material in once producing, just can complete batch mixing, mixing, plasticizing, shear disperse, the whole process of homogenizing and dehydration, on this basis, the further span of control of its main operating parameters is: engine speed 150-300 rev/min, feeding machine rotating speed 8-30 rev/min; Extrusion temperature span of control: one to three district 140-145 DEG C, four to six district 169-175 DEG C, seven to ten district 140-145 DEG C; Through the thermostat container constant temperature of 70-80 DEG C, thermostat container adopts hot blast constant temperature, avoids the deformation that water-cooled causes, drawn, batches and obtain the even thread lactic acid composite material of diameter at about 1.75mm.
3. according to a kind of described in claim 2 preparation method of the lactic acid composite material for 3 D-printing, it is characterized in that: preparation method the 1st) pulverizing mill described in step is vertical air-flow pulverizing mill, under the impact that high velocity air is formed, sheet fine metal powder is fluidization, each fine powder is made to have single kinestate, realize disperseing also and coating materials activation modification sheet fine metal powder boundling, thus form activating sheet micro-fine metal powder.
4. according to a kind of described in claim 2 preparation method of the lactic acid composite material for 3 D-printing, it is characterized in that: preparation method the 3rd) screw extruder described in step is parallel dual-screw extruding machine.
5. according to a kind of described in claim 2 preparation method of the lactic acid composite material for 3 D-printing, it is characterized in that: preparation method the 3rd) the preferred length-to-diameter ratio of screw extruder described in step is at 20-25
:the parallel dual-screw extruding machine of 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105348496A (en) * | 2015-12-17 | 2016-02-24 | 昆山天洋热熔胶有限公司 | Composite consumable suitable for 3D printing and preparation method thereof |
| CN105801819A (en) * | 2016-06-01 | 2016-07-27 | 昆山天洋热熔胶有限公司 | Copolyester suitable for serving as 3D printing material and preparation method thereof |
| CN106317811A (en) * | 2016-08-16 | 2017-01-11 | 西安建筑科技大学 | Method for making stainless steel texture component in building landscape model by 3D printing |
| CN107974062A (en) * | 2017-11-03 | 2018-05-01 | 金发科技股份有限公司 | A kind of polylactic acid 3D printing material and wire rod prepared therefrom |
| CN108676336A (en) * | 2018-05-29 | 2018-10-19 | 共享智能铸造产业创新中心有限公司 | Lactic acid composite material and preparation method thereof applied to FDM forming techniques |
| CN109265940A (en) * | 2018-07-26 | 2019-01-25 | 嘉善天惠服饰有限公司 | One kind is for degradable PLA Biocomposite material of garment accessories and preparation method thereof |
| CN110430992A (en) * | 2017-03-17 | 2019-11-08 | 日东电工株式会社 | Moulding pad |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834862A (en) * | 2014-03-24 | 2014-06-04 | 广东省钢铁研究所 | Iron-cobalt alloy and preparation method of magnetizing pole head of iron-cobalt alloy |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103834862A (en) * | 2014-03-24 | 2014-06-04 | 广东省钢铁研究所 | Iron-cobalt alloy and preparation method of magnetizing pole head of iron-cobalt alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105348496A (en) * | 2015-12-17 | 2016-02-24 | 昆山天洋热熔胶有限公司 | Composite consumable suitable for 3D printing and preparation method thereof |
| CN105801819A (en) * | 2016-06-01 | 2016-07-27 | 昆山天洋热熔胶有限公司 | Copolyester suitable for serving as 3D printing material and preparation method thereof |
| CN105801819B (en) * | 2016-06-01 | 2018-05-11 | 昆山天洋热熔胶有限公司 | A kind of copolyesters for being adapted as 3D printing material and preparation method thereof |
| CN106317811A (en) * | 2016-08-16 | 2017-01-11 | 西安建筑科技大学 | Method for making stainless steel texture component in building landscape model by 3D printing |
| CN106317811B (en) * | 2016-08-16 | 2018-07-10 | 西安建筑科技大学 | The method that stainless steel texture component in architecture visual model is made using 3D printing |
| CN110430992A (en) * | 2017-03-17 | 2019-11-08 | 日东电工株式会社 | Moulding pad |
| CN107974062A (en) * | 2017-11-03 | 2018-05-01 | 金发科技股份有限公司 | A kind of polylactic acid 3D printing material and wire rod prepared therefrom |
| CN108676336A (en) * | 2018-05-29 | 2018-10-19 | 共享智能铸造产业创新中心有限公司 | Lactic acid composite material and preparation method thereof applied to FDM forming techniques |
| CN109265940A (en) * | 2018-07-26 | 2019-01-25 | 嘉善天惠服饰有限公司 | One kind is for degradable PLA Biocomposite material of garment accessories and preparation method thereof |
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Effective date of registration: 20170110 Address after: On the new village 519000 West Street in Guangdong city of Zhuhai Province, No. 38, 2 floor of Building 2 room 208 Patentee after: Zhuhai Golden Camel Technology Co., Ltd. Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Patentee before: Sichuan Chengdu New Keli Chemical Technology Co., Ltd. |