CN104845300B - A kind of lactic acid composite material for 3 D-printing and preparation method thereof - Google Patents
A kind of lactic acid composite material for 3 D-printing and preparation method thereof Download PDFInfo
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Abstract
The present invention proposes a kind of lactic acid composite material for 3 D-printing, it is characterized in that: containing lamellar micro-fine metal powder, it is prepared from by the raw material of following components by weight: polylactic acid 70 80 parts, lamellar micro-fine metal powder 5 15 parts, coating material 12 parts, crystallizing agent 0.5 1 parts, 0.2 0.3 parts of antioxidant, processing aid 0.2 0.3 parts；By introducing the lamellar micro-fine metal powder with flexible and good thermal capacitance in polylactic acid, utilize the thermal capacitance of lamellar micro-fine metal powder thus change the hot property of polylactic acid, prevent polylactic acid from quickly cooling down and deform upon.Especially flake metal powder has good sliding and pliability, makes the flow uniformity of polylactic acid and toughness be improved, and is adapted to manufacture high accuracy goods by 3 D-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 further to the preparation method of this lactic acid composite material.
Background technology
3D printing technique is a kind of quickly increasing material manufacturing technology generating 3D solid by successively increasing accumulation material, not only overcomes tradition and subtracts the loss that material manufacture causes, and makes product manufacturing more intelligent, precisely, more more efficient.3D prints manufacturing technology and represents the new trend of world's development of manufacturing, for accelerating advanced manufacturing industry development, promoting that industrial repositioning upgrading has important leading action.Along with high-end manufacturing development, current 3D prints manufacturing technology and is paid high attention to, and is collectively known as promoting the key technology of the third time industrial revolution with robotics, artificial intelligence technology.
Changing molding mode and the principle of product completely owing to 3D prints manufacturing technology, be to overturn conventionally manufactured pattern, therefore material bottleneck becomes the problem limiting 3D printing development, is also key point and the difficult point place of 3D printing 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 at shower nozzle, solidification forms the thin layer of contour shape, forms product by the accumulation that is layering of thin layer.The most conventional melted extrusion modeling molded polymer material has acrylonitrile-butadiene-styrene terpolymer (ABS), polylactic acid (PLA), nylon (PA) etc..
Due to the good thermal fluidity of polymeric material, quickly cool down cementability, higher mechanical strength, print manufacture field at 3D and quickly applied and develop.Especially polylactic acid has characteristic nontoxic, without pungent abnormal smells from the patient, has obtained good application in 3D printed material.But due to fused glass pellet technique it is crucial that keep half mobility of material, even solidification molding, and polylactic acid is a kind of crystal structure, directly convert to liquid from solid during heating, temperature reduces then rapid solidification, therefore during cooling, nozzle phase change is big, easily plug nozzle, there is buckling deformations in the product of formation.The especially crystallographic rigidity of polylactic acid, lack toughness when causing polylactic acid as 3D printing consumables easily to break, it is impossible to long-time stable molding, cause printing to have some setbacks, the product lacking toughness of molding and intensity, the product making polylactic acid print is very restricted in terms of precision, intensity.
China Patent Publication No. CN103146164A
Disclosing a kind of poly-lactic acid material nano material toughened for rapid shaping and preparation method thereof, the method is to utilize double screw extruder that polyacrylic acid ester microsphere and polylactic acid are carried out blending extrusion toughening modifying.
China Patent Publication No. CN103087489A
Disclosing a kind of modified polylactic acid material and preparation method thereof, the method polyether polyamide elastomer and montmorillonite, as modifying agent, do modified device with double screw extruder, enhance hot strength and the toughness of polylactic acid.
China Patent Publication No. CN102134381A
Disclose a kind of modified polylactic acid material and preparation method thereof, by toughness reinforcing heat-resistant elastomer modifying agent and polylactic acid blend extrusion modification in the method, i.e. improve the defect of the poor toughness of polylactic acid, also improve the heat resisting temperature of polylactic acid.
When 3D prints melted extrusion modeling molding, it is desirable to material has good thermal transition performance, i.e. can become half flowable state, the most uniform molding, even solidification during cooling during heating, prevent thermal contraction from deforming.According to above-mentioned, blending and modifying to polylactic acid at present, its toughness is made to be improved by increasing toughening material, but thermal transition characteristic the most substantially changes, and has definite melting point because of polylactic acid during heating, directly convert to liquid from solid, successively easily trickle during molding, temperature reduces then rapid solidification, and therefore thermal contraction deformation is big, it is difficult to print high accuracy goods.
Summary of the invention
Polylactic acid is because having crystallinity definite melting point when 3D printing consumables at present, easily trickles during melted extrusion modeling molding, and temperature reduces then rapid solidification, causes 3D to print difficulty, and thermal contraction deformation is big, it is difficult to print high accuracy goods.For this defect, the present invention proposes a kind of lactic acid composite material for 3 D-printing.By introducing lamellar micro-fine metal powder in polylactic acid, utilizing the thermal capacitance of lamellar micro-fine metal powder thus change the hot property of polylactic acid, making during polylactic acid melted extrusion modeling molding is semifluid, prevent trickling, when molding cools down, uniformly, thermal contraction diminishes, and prevents from warping in solidification；Further, lamellar micro-fine metal powder has good sliding and pliability, promotes polylactic acid Uniform Flow when 3 D-printing, is adapted to print high accuracy goods.
Further, it is provided that the preparation method of a kind of lactic acid composite material for 3 D-printing.
A kind of lactic acid composite material for 3 D-printing, is achieved by the following technical solution:
A kind of lactic acid composite material for 3 D-printing, is characterized in that: containing lamellar micro-fine metal powder, be prepared from by the raw material of following components by weight:
Polylactic acid
70-80 part,
Lamellar micro-fine metal powder 5-15 part,
Coating material 1-2 part,
Crystallizing agent 0.5-1 part,
Antioxidant 0.2-0.3 part,
Processing aid 0.2-0.3 part,
Described polylactic acid is number-average molecular weight 10-15 ten thousand, and the powder polylactic acid sieved by 50 mesh, at 190 DEG C × 2.16kg
Test condition under melt index be 4-6g/10min；
Described lamellar micro-fine metal powder is mean diameter 10-20 μm, and radius-thickness ratio is more than at least one in the fine flake aluminum of 20, fine zinc flake, fine flake iron powder, fine lamellar stainless steel powder, fine Nickel Powder, fine lamellar titanium valve, fine flake copper, fine lamellar zinc aluminium alloy powder；
Described coating material is at least one in stearic acid sorbitan ester, single Palmic acid sorbitan ester, sorbitan monooleate, polyoxyethylene sorbitan monooleate dehydration；
Described crystallizing agent is poly(ethylene oxide)；
Described antioxidant 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 compounding form by weight 1: 1；
Described processing aid is at least one in N, N '-bis-ethylene hard fatty acids amide, stearic amide, paraffin, Tissuemat E, polypropylene 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 as follows:
1) the lamellar micro-fine metal powder of 5-15 weight portion, the coating material of 1-2 weight portion are joined in pulverizing mill, set pulverizing mill temperature 80-100 DEG C, with 1200-1500rpm speed high speed dispersion 5-10min, lamellar fine metal powder body boundling is dispersed throughout, the antioxidant being subsequently adding 0.2-0.3 weight portion continues dispersion 3-5min, obtains active lamellar fine metal powder body；
2) active sheet fine metal powder body step 1) obtained adds high-speed mixer with the crystallizing agent of the polylactic acid powder of 70-80 weight portion, 0.5-1 weight portion, under the conditions of 40-50 DEG C, rotating speed mixing 10-20min with 300-900rpm, it is subsequently adding processing aid dispersion mixing 3-5min of 0.2-0.3 weight portion, blowing after the completely melted dispersion of processing aid；
3) by step 2) material that obtains is placed in screw extruder, extrude under the conditions of 140-175 DEG C, form circular bar by the single hole mould that aperture is 3mm, through the calorstat constant temperature after-drawing of 70-80 DEG C, batch the uniform thread lactic acid composite material obtaining diameter at about 1.75mm.
Above-mentioned preparation method the 1st) pulverizing mill described in step is vertical air-flow pulverizing mill, it is made up of with moving knife stationary knife, the moving knife of high speed rotating forms high velocity air, under the impact that high velocity air is formed, lamellar fine metal powder body is fluidization, each fine powder is made to have single kinestate, realize to lamellar fine metal powder body boundling dispersion and with coating material activation modification, thus form activating sheet micro-fine metal powder, lamellar activated fine metal powder has higher radius-thickness ratio, two-dimension plane structure, not only sliding capability is excellent, and there is good pliability and thermal capacitance.
Above-mentioned preparation method the 2nd) high-speed mixer described in step uses 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 stirring 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 polylactic acid, the most more preferably parallel dual-screw extruding machine draw ratio is at 20-25:1, be provided with vacuum volatilization device, make material just can complete in once producing batch mixing, mixing, plastify, shear the overall process of dispersion, homogenizing and dehydration, melt time of staying in machine barrel is short, decreases the thermal degradation of polylactic 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 140-145 DEG C of district, four to six 169-175 DEG C of districts, seven to ten 140-145 DEG C of districts.
Above-mentioned preparation method the 3rd) calorstat described in step uses hot blast constant temperature, avoiding the deformation that water-cooled causes, under the conditions of 70-80 DEG C, lactic acid composite material has good viscoelasticity, 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 lamellar micro-fine metal powder with flexible and good thermal capacitance in polylactic acid, utilize the thermal capacitance of lamellar micro-fine metal powder thus change the hot property of polylactic acid, when 3 D-printing preheats, lamellar micro-fine metal powder storage amount of heat, polylactic acid makes polylactic acid form semifluid by flake metal powder progressively heat release during three-dimensional melted extrusion modeling molding, prevent trickling, the flake metal powder heat absorption when molding cools down, and make polylactic acid be in viscoelastic state, prevent polylactic acid from quickly cooling down and deform upon.Especially flake metal powder has good sliding, is dispersed in polylactic acid and promotes polylactic acid uniform flow when by the melted nozzle of 3 D-printing；Lamellar micro-fine metal powder has pliability, makes the toughness of polylactic acid be improved.Therefore, the present invention is adapted to print high accuracy 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, the high velocity air formed by pulverizing mill, each fine powder is made to have single kinestate, realize to fine metal sheet powder body boundling dispersion and with coating material activation modification, thus form activated fine sheet metal, make to have higher radius-thickness ratio, the fine metal sheet of two-dimension plane structure is dispersed in polylactic acid, and not only sliding capability is excellent, and has good pliability and thermal capacitance.Used by hot blast constant temperature, it is to avoid the deformation that water-cooled causes, under the conditions of 70-80 DEG C, lactic acid composite material has good viscoelasticity, can carry out uniform and stable stretching, the thread polylactic 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 prominent 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 hot property of polylactic acid, when this lactic acid composite material carries out melt extruded 3 D-printing, the flake metal powder contained progressively heat release makes polylactic acid form semifluid, prevents trickling, the flake metal powder heat absorption when molding cools down, and make polylactic acid be in viscoelastic state, prevent polylactic acid from quickly cooling down and deform upon.
2, a kind of lactic acid composite material for 3 D-printing of the present invention, has a good sliding containing flake metal powder, promotes polylactic acid uniform flow when by the melted nozzle of 3 D-printing；Lamellar micro-fine metal powder has pliability, makes the toughness of polylactic acid be improved.This lactic acid composite material is adapted to 3 D-printing high accuracy goods.
3, the preparation method of a kind of lactic acid composite material for 3 D-printing of the present invention, the high velocity air formed by pulverizing mill, each fine powder is made to have single kinestate, realize to fine metal sheet powder body boundling dispersion and with coating material activation modification, thus form activated fine sheet metal, make to have higher radius-thickness ratio, the fine metal sheet of two-dimension plane structure is dispersed in polylactic acid, and not only sliding capability is excellent, and has good pliability and thermal capacitance.
4, the preparation method of a kind of lactic acid composite material for 3 D-printing of the present invention, used by hot blast constant temperature, avoid the deformation that water-cooled causes, under the conditions of 70-80 DEG C, lactic acid composite material has good viscoelasticity, can carry out uniform and stable stretching, the polylactic acid composite filament circularity obtained is controlled within positive and negative 0.02mm.
Detailed description of the invention
Below by way of detailed description of the invention, the present invention is described in further detail, but this should not being interpreted as, the scope of the present invention is only limitted to Examples below.In the case of without departing from said method thought of the present invention, the various replacements made according to ordinary skill knowledge and customary means or change, should be included in the scope of the present invention.
Embodiment 1
1) by the fine flake aluminum of 5 weight portions, the coating material stearic acid sorbitan ester of 2 weight portions joins in pulverizing mill, set pulverizing mill temperature 80 DEG C, with 1200rpm speed high speed dispersion 5min, lamellar fine metal powder body boundling is dispersed throughout, it is subsequently adding 0.2 weight portion 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) the compounding antioxidant of ester by weight 1: 1, continue dispersion 3-5min, obtain active lamellar fine metal powder body；
2) poly(ethylene oxide) of active sheet fine metal powder body step 1) obtained and the polylactic acid powder of 70 weight portions, 0.5 weight portion adds high-speed mixer, under the conditions of 40 DEG C, rotating speed mixing 10min with 300rpm, it is subsequently adding polypropylene wax dispersion mixing 5min of 0.2 weight portion, blowing after the completely melted dispersion of processing aid；
3) by step 2) material that obtains is placed in draw ratio 25:The parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material just can complete in once producing batch mixing, mixing, plastify, shear the overall process of dispersion, 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 140-145 DEG C of district, four to six 169-175 DEG C of districts, seven to ten 140-145 DEG C of districts, form circular bar by the single hole mould that aperture is 3mm, through the calorstat constant temperature after-drawing of 70-80 DEG C, batch the uniform thread lactic acid composite material obtaining diameter at about 1.75mm.
The thread lactic acid composite material performance data such as following table that embodiment 1 is obtained:
| Inspection project | Testing result |
| Average diameter (mm) | 1.75 |
| Diameter tolerance (mm) | ±0.02 |
| Hot strength (MPa) | 2.82 |
| Melt temperature | 175℃ |
| Solution flow index (g/10min) | 8 |
| Condensation 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 the conditions of 175 DEG C, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and design error, within ± 0.1mm, are adapted to print high accuracy goods.
Embodiment 2
1) by the fine zinc flake of 10 weight portions, the coating material list Palmic acid sorbitan ester of 1.5 weight portions joins in pulverizing mill, set pulverizing mill temperature 85 DEG C, with 1500rpm speed high speed dispersion 10min, lamellar fine metal powder body boundling is dispersed throughout, it is subsequently adding 0.2 weight portion 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) the compounding antioxidant of ester by weight 1: 1, continue dispersion 4min, obtain active lamellar fine metal powder body；
2) the crystallizing agent poly(ethylene oxide) of active sheet fine metal powder body step 1) obtained and the polylactic acid powder of 75 weight portions, 1 weight portion adds high-speed mixer, under the conditions of 45 DEG C, rotating speed mixing 15min with 500rpm, it is subsequently adding processing aid Tissuemat E dispersion mixing 5min of 0.3 weight portion, blowing after the completely melted dispersion of processing aid；
3) by step 2) material that obtains is placed in draw ratio 20:The parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material just can complete in once producing batch mixing, mixing, plastify, shear the overall process of dispersion, 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 140-145 DEG C of district, four to six 169-175 DEG C of districts, seven to ten 140-145 DEG C of districts, form circular bar by the single hole mould that aperture is 3mm, through the calorstat constant temperature after-drawing of 70-80 DEG C, batch the uniform thread lactic acid composite material obtaining diameter at about 1.74mm.
The thread lactic acid composite material performance data such as following table that embodiment 2 is obtained:
| Inspection project | Testing result |
| Average diameter (mm) | 1.74 |
| Diameter tolerance (mm) | ±0.02 |
| Hot strength (MPa) | 2.66 |
| Melt temperature | 175℃ |
| Solution flow index (g/10min) | 8.6 |
| Condensation 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 the conditions of 175 DEG C, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and design error, within ± 0.1mm, are adapted to print high accuracy goods.
Embodiment 3
1) by the fine lamellar zinc aluminium alloy powder of 15 weight portions, the coating material sorbitan monooleate of 2 weight portions joins in pulverizing mill, set pulverizing mill temperature 100 DEG C, with 1300rpm speed high speed dispersion 10min, lamellar fine metal powder body boundling is dispersed throughout, it is subsequently adding 0.3 weight portion 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) the ester antioxidant continuation dispersion 3min that compound at 1: 1 by weight, obtain active lamellar fine metal powder body；
2) the crystallizing agent poly(ethylene oxide) of active sheet fine metal powder body step 1) obtained and the polylactic acid powder of 80 weight portions, 0.5 weight portion adds high-speed mixer, under the conditions of 50 DEG C, rotating speed mixing 20min with 900rpm, it is subsequently adding the processing aid N of 0.2 weight portion, N '-bis-ethylene hard fatty acids amide dispersion mixings 5min, blowing after the completely melted dispersion of processing aid；
3) by step 2) material that obtains is placed in draw ratio 25:The parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material just can complete in once producing batch mixing, mixing, plastify, shear the overall process of dispersion, 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 140-145 DEG C of district, four to six 169-175 DEG C of districts, seven to ten 140-145 DEG C of districts, form circular bar by the single hole mould that aperture is 3mm, through the calorstat constant temperature after-drawing of 70-80 DEG C, batch the uniform thread lactic acid composite material obtaining 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 the conditions of 175 DEG C, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and design error, within ± 0.1mm, are adapted to print high accuracy goods.
Embodiment 4
1) by the fine flake iron powder of 15 weight portions, the coating material polyoxyethylene sorbitan monooleate dehydration of 2 weight portions joins in pulverizing mill, set pulverizing mill temperature 90 DEG C, with 1200rpm speed high speed dispersion 10min, lamellar fine metal powder body boundling is dispersed throughout, it is subsequently adding 0.3 weight portion 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) the ester antioxidant continuation dispersion 3min that compound at 1: 1 by weight, obtain active lamellar fine metal powder body；
2) the crystallizing agent poly(ethylene oxide) of active sheet fine metal powder body step 1) obtained and the polylactic acid powder of 70 weight portions, 0.5 weight portion adds high-speed mixer, under the conditions of 50 DEG C, rotating speed mixing 10min with 400rpm, it is subsequently adding processing aid stearic amide dispersion mixing 3min of 0.2 weight portion, blowing after the completely melted dispersion of processing aid；
3) by step 2) material that obtains is placed in draw ratio 20:The parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material just can complete in once producing batch mixing, mixing, plastify, shear the overall process of dispersion, 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 140-145 DEG C of district, four to six 169-175 DEG C of districts, seven to ten 140-145 DEG C of districts, form circular bar by the single hole mould that aperture is 3mm, through the calorstat constant temperature after-drawing of 70-80 DEG C, batch the uniform thread lactic acid composite material obtaining 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 the conditions of 175 DEG C, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and design error, within ± 0.1mm, are adapted to print high accuracy goods.
Embodiment 5
1) by the fine Nickel Powder of 10 weight portions, the coating material sorbitan monooleate of 1 weight portion joins in pulverizing mill, set pulverizing mill temperature 100 DEG C, with 1300rpm speed high speed dispersion 10min, lamellar fine metal powder body boundling is dispersed throughout, it is subsequently adding 0.3 weight portion 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) the ester antioxidant continuation dispersion 3min that compound at 1: 1 by weight, obtain active lamellar fine metal powder body；
2) the crystallizing agent poly(ethylene oxide) of active sheet fine metal powder body step 1) obtained and the polylactic acid powder of 80 weight portions, 0.5 weight portion adds high-speed mixer, under the conditions of 50 DEG C, rotating speed mixing 20min with 900rpm, it is subsequently adding the processing aid N of 0.2 weight portion, N '-bis-ethylene hard fatty acids amide dispersion mixings 5min, blowing after the completely melted dispersion of processing aid；
3) by step 2) material that obtains is placed in draw ratio 25:The parallel dual-screw extruding machine of 1, be provided with vacuum volatilization device, make material just can complete in once producing batch mixing, mixing, plastify, shear the overall process of dispersion, 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 140-145 DEG C of district, four to six 169-175 DEG C of districts, seven to ten 140-145 DEG C of districts, form circular bar by the single hole mould that aperture is 3mm, through the calorstat constant temperature after-drawing of 70-80 DEG C, batch the uniform thread lactic acid composite material obtaining 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 the conditions of 175 DEG C, uniform and stable flowing, realize stable printing, the goods printed do not trickle, cooling stable and uniform, the goods obtained and design error, within ± 0.1mm, are adapted to print high accuracy goods.
Claims (5)
1., for a lactic acid composite material for 3 D-printing, it is characterized in that: containing lamellar micro-fine metal powder, be by weight mainly made up of the raw material of following components:
Polylactic acid 70-80 part,
Lamellar micro-fine metal powder 5-15 part,
Coating material 1-2 part,
Crystallizing agent 0.5-1 part,
Antioxidant 0.2-0.3 part,
Processing aid 0.2-0.3 part,
Described polylactic acid is number-average molecular weight 10-15 ten thousand, the powder polylactic acid sieved by 50 mesh, and under the test condition of 190 DEG C × 2.16kg, melt index is 4-6g/10min；
Described lamellar micro-fine metal powder is mean diameter 10-20 μm, and radius-thickness ratio is more than at least one in the fine flake aluminum of 20, fine zinc flake, fine flake iron powder, fine lamellar stainless steel powder, fine Nickel Powder, fine lamellar titanium valve, fine flake copper, fine lamellar zinc aluminium alloy powder；
Described coating material is at least one in stearic acid sorbitan ester, single Palmic acid sorbitan ester, sorbitan monooleate, polyoxyethylene sorbitan monooleate dehydration；
Described crystallizing agent is poly(ethylene oxide)；
Described antioxidant 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 compounding form by weight 1: 1；
Described processing aid is at least one in N, N '-bis-ethylene hard fatty acids amide, stearic amide, paraffin, Tissuemat E, polypropylene wax.
2. the method preparing the lactic acid composite material for 3 D-printing as claimed in claim 1, is characterized in that processing the raw material of the weight ratio described in claim 1 as follows:
1) the lamellar micro-fine metal powder of 5-15 weight portion, the coating material of 1-2 weight portion are joined in pulverizing mill, set pulverizing mill temperature 80-100 DEG C, with 1200-1500rpm speed high speed dispersion 5-10min, lamellar fine metal powder body boundling is dispersed throughout, the antioxidant being subsequently adding 0.2-0.3 weight portion continues dispersion 3-5min, obtains active lamellar fine metal powder body；
2) active sheet fine metal powder body step 1) obtained adds high-speed mixer with the crystallizing agent of the polylactic acid powder of 70-80 weight portion, 0.5-1 weight portion, under the conditions of 40-50 DEG C, rotating speed mixing 10-20min with 300-900rpm, it is subsequently adding processing aid dispersion mixing 3-5min of 0.2-0.3 weight portion, blowing after the completely melted dispersion of processing aid；
3) by step 2) material that obtains is placed in screw extruder, extrude under the conditions of 140-175 DEG C, circular bar is formed by the single hole mould that aperture is 3mm, screw extruder is provided with vacuum volatilization device, make material complete in once producing batch mixing, mixing, plastify, shear the overall process of dispersion, 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 140-145 DEG C of district, four to six 169-175 DEG C of districts, seven to ten 140-145 DEG C of districts；Through the calorstat constant temperature of 70-80 DEG C, calorstat uses hot blast constant temperature, it is to avoid the deformation that water-cooled causes, drawn, batches the uniform thread lactic acid composite material obtaining diameter at 1.75mm.
3. according to the preparation method of the lactic acid composite material for 3 D-printing a kind of described in claim 2, 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, lamellar fine metal powder body is fluidization, each fine powder is made to have single kinestate, realize to the dispersion of lamellar fine metal powder body boundling and with coating material activation modification, thus form activating sheet micro-fine metal powder.
4. according to the preparation method of the lactic acid composite material for 3 D-printing a kind of described in claim 2, it is characterised in that: preparation method the 3rd) screw extruder described in step is parallel dual-screw extruding machine.
5. according to the preparation method of the lactic acid composite material for 3 D-printing a kind of described in claim 2, it is characterised in that: preparation method the 3rd) screw extruder draw ratio described in step is at 20-25:The parallel dual-screw extruding machine of 1.
Priority Applications (1)
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| CN105348496B (en) * | 2015-12-17 | 2018-02-27 | 昆山天洋热熔胶有限公司 | A kind of compound consumptive material suitable for 3D printing 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 |
| 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 |
| JP6989272B2 (en) * | 2017-03-17 | 2022-01-05 | 日東電工株式会社 | Molding mat |
| CN107974062B (en) * | 2017-11-03 | 2020-10-09 | 金发科技股份有限公司 | Polylactic acid 3D printing material and wire prepared from same |
| 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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| 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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