CN115895218A - Polycaprolactone magnesium ceramic composite 3D printing wire and preparation method thereof - Google Patents
Polycaprolactone magnesium ceramic composite 3D printing wire and preparation method thereof Download PDFInfo
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 84
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000011777 magnesium Substances 0.000 title claims abstract description 52
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 52
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 238000010146 3D printing Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000004898 kneading Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 31
- 239000000155 melt Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 9
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 9
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000011268 mixed slurry Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 230000017455 cell-cell adhesion Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a polycaprolactone magnesium ceramic composite 3D printing wire and a preparation method thereof, wherein the printing wire comprises the following components in parts by mass: 65-95% of PCL pure material, 4-30% of magnesium ceramic powder and 0.1-5% of good solvent of polycaprolactone. The main innovation points of the invention are as follows: the PCL-magnesium ceramic composite 3D printing material adopts a good solvent of polycaprolactone to carry out surface treatment, a pre-mixed slurry side feeding process, integrated kneading and banburying and other key technical means on magnesium ceramic powder, and effectively solves the problems of poor compatibility, low yield of finished products and the like of the PCL-magnesium ceramic composite 3D printing material.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polycaprolactone magnesium ceramic composite 3D printing wire and a preparation method thereof.
Background
The 3D printing technology has been widely used in the fields of industry, medical treatment, and the like in recent years. In particular, tissue repair in medical applications requires highly customized devices to be prepared according to specific conditions, and is very suitable for the exertion of 3D printing technology. Among them, the magnesium ceramic material has received important attention in the field as one of key materials for bone repair, and there are many studies reporting 3D printing and application of the magnesium ceramic material, such as chinese invention application CN111407927B, "a magnesium silicate/polyamino acid composite material capable of being clinically shaped and its use in preparing bone repair material", and the like. However, the 3D printing technology for ceramic materials is still immature, the commercial printer is expensive, the types of printable ceramic powder are few, and the requirements of composite application of various medical magnesium ceramic materials cannot be met.
The 3D printing technology comprises methods such as Fused Deposition Modeling (FDM) and powder sintering modeling, wherein the fused deposition modeling has the advantages of being simple to operate, low in equipment cost, easy to replace consumable materials and the like. With the development of the melt-deposition molding technology, the polymer-ceramic powder composite wire is mature day by day, and the melt-deposition printing of the polymer and ceramic powder composite material can replace the powder sintering printing scheme with high equipment cost and high requirements on the performance of the printing material under some conditions, so that the preparation of the magnesium ceramic polymer composite wire is used in the field of bone repair 3D printing and naturally becomes an easily-conceived technical means. For example, the Chinese invention application CN113827777A reports a three-dimensional porous composite scaffold material and a preparation method thereof, polylactic acid-nano hydroxyapatite-nano magnesium oxide is adopted as an FDM 3D printing material.
However, reports on such technical schemes are very rare so far, because the density, mechanical properties and the like of the high polymer material and the magnesium ceramic powder are relatively different, and the compatibility is poor during blending granulation; the addition of the magnesium ceramic powder affects the viscosity of the polymer matrix material when the polymer matrix material is melted, and thus affects the diameter control, the surface roughness and the like of the 3D printing wire.
Polycaprolactone (PCL) is a compound which has good compatibility with biological cells and can be degraded into CO 2 And H 2 O, environmental protection and biological materials. Compared with the main stream degradable 3D printing material polylactic acid, the polycaprolactone has the excellent performances that the degradation product is weaker in acidity, the biological tissue is milder, the glass transition temperature (-60 ℃) and the melting point (60 ℃ -63 ℃) are lower, the low-temperature forming is easy, and the like, and the polycaprolactone is more suitable for being applied to in-vivo implanted devices. Therefore, PCL is compounded with magnesium-based materials, is used in the fields of bone repair, bone tissue engineering and the like, and is also a research hotspot in recent years, for example, U.S. Pat. No. 4,989,989/0024244, 0024244 Al reports a technology of magnesium fluoride and PCL double-layer coating magnesium alloy plate, compared with a magnesium fluoride single-layer coating sample or an uncoated magnesium sample, the corrosion resistance is improved, and the PCL has excellent cell viability, cell adhesion and cell proliferation. However, polycaprolactone is soft, so that the printing difficulty of the polycaprolactone is higher when the polycaprolactone is used for FDM, the requirement on a forming process for preparing the wire is higher, and the preparation of the polymer-metal composite wire by further adding components such as alloy powder is more difficult, so that the PCL-magnesium ceramic composite 3D printing material is not reported.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and effectively solves the problems of poor compatibility, low finished product yield and the like of the PCL-magnesium ceramic composite 3D printing material by adopting key technical means of surface treatment, premixed slurry side feeding process, integrated kneading and banburying and the like of the good solvent of polycaprolactone on magnesium ceramic powder.
In order to achieve the above object, in a first aspect, the invention provides a polycaprolactone magnesium ceramic composite 3D printing wire, which comprises the following components by mass: 65-95% of PCL pure material, 4-30% of magnesium ceramic powder and 0.1-5% of good solvent of polycaprolactone.
In the polycaprolactone magnesium ceramic composite 3D printing wire, the magnesium ceramic is one or more of magnesium oxide, magnesium fluoride, magnesium titanate, magnesium hydroxide, basic magnesium carbonate, olivine (calcium magnesium silicate) and dolomite (calcium magnesium carbonate), and the powder particle size range is 0.2 μm to 500 μm.
In a second aspect, the invention also provides a preparation method of the polycaprolactone magnesium ceramic composite 3D printing wire, which comprises the following steps: (1) respectively weighing the following components in parts by mass: 65% -95% of PCL pure material, 4% -30% of magnesium ceramic powder and 0.1% -5% of good polycaprolactone solvent, wherein the PCL pure material is divided into three parts; (2) Adding a good solvent of polycaprolactone into the magnesium ceramic powder, and mixing and stirring to prepare slurry; (3) Mixing the first part of PCL pure material with the magnesium ceramic powder slurry obtained in the step (2), and then feeding the mixture into a side feeding system of a double-screw extruder, and feeding the second part of PCL pure material into a main feeding system of the double-screw extruder to extrude a melt; (4) After the melt is extruded by the extruder, further kneading and uniformly mixing the melt by adopting an integrated kneading internal mixer, uniformly distributing the magnesium alloy micro powder in the melt, and then granulating to obtain composite master batches; (5) And drying the composite master batch, blending the dried composite master batch with a third part of pure PCL, and extruding by using a single screw to obtain the PCL-magnesium ceramic composite 3D printing wire.
In the preparation method of the polycaprolactone-magnesium-ceramic composite 3D printing wire, the good solvent of polycaprolactone used in the step (2) is one or more of polar solvents such as toluene, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, hexafluoroisopropanol and the like.
In the preparation method of the polycaprolactone magnesium ceramic composite 3D printing wire, the specific process of preparing the slurry in the step (2) is as follows: putting the raw materials into a high-speed mixer, and fully stirring and mixing for 2-5 min.
In the preparation method of the polycaprolactone magnesium ceramic composite 3D printing wire, the double-screw extrusion processing temperature in the step (3) is 80-135 ℃.
In the preparation method of the polycaprolactone magnesium ceramic composite 3D printing wire, the single-screw extrusion processing temperature in the step (5) is 80-135 ℃.
In the preparation method of the polycaprolactone magnesium ceramic composite 3D printing wire, the PCL pure material is added in three parts of the main feeding material of the double-screw extruder, the side feeding material of the double-screw extruder and the main feeding material of the single-screw extruder.
Compared with the prior art, the invention has the following beneficial effects:
the magnesium ceramic powder is pretreated by utilizing the good solvent of the polycaprolactone, so that the compatibility between the powder and the PCL material can be improved; by adopting the scheme that the slurry and part of the PCL pure material are fed into the PCL feeding port at the same side, the problems of bridging, blockage and the like of the slurry at the main feeding port can be prevented, and the dispersibility of the magnesium ceramic powder in the PCL can be effectively improved, so that the problems of poor dispersibility, poor mechanical property, low product yield and the like of the composite material are solved.
Detailed Description
The present invention will now be described in further detail with reference to examples, but the present invention is not limited to the following examples, and any modifications made thereto will fall within the scope of the present invention.
Example 1:
the utility model provides a compound 3D of polycaprolactone magnesium oxide prints wire rod, contains following mass component: 70% of PCL, 28% of magnesium oxide powder and 2% of dichloromethane.
The particle size of the magnesium oxide powder is 200 +/-20 mu m.
The preparation method comprises the following steps: (1) Mixing 2 parts of dichloromethane and 28 parts of magnesium oxide powder, putting the mixture into a high-speed mixer, and fully stirring and mixing the mixture for 2 to 5 minutes to prepare slurry; (2) Mixing 20 parts of PCL pure material and magnesium oxide powder slurry according to corresponding parts to prepare side feeding material; (3) Extruding the side feeding material and 20 parts of pure PCL material into a melt through a side feeding system of a double-screw extruder, wherein the processing temperature is 135 ℃; (4) After the melt is extruded by the extruder, further kneading and uniformly mixing the melt by adopting an integrated kneading internal mixer, uniformly distributing the magnesium alloy micro powder in the melt, and then granulating to obtain composite master batches; (5) And drying the composite master batch, mixing the dried composite master batch with 30 parts of pure PCL (polycaprolactone), and extruding the mixture by using a single screw to obtain the composite 3D printing wire rod, wherein the processing temperature is 135 ℃.
The total content of PCL in the wire rod is 70%, the wire rod is smooth through testing, the diameter of the wire rod is 1.75 +/-0.02 mm, the texture of the wire rod is similar to that of an inorganic material, the printing effect is good, and the actual measurement yield of a printed product is more than 95%.
The resulting material was 3D printed as standard splines and tested for tensile properties (GB [0031] T1040.2-2006), flexural strength (GB/T1446-2006) and impact properties (GB/T1943-2008), respectively, with the test results shown in Table 1.
Example 2:
the utility model provides a compound 3D of polycaprolactone magnesium fluoride prints wire rod, contains the following mass component: 65% of PCL, 30% of magnesium fluoride powder and 5% of trichloromethane.
The particle size range of the magnesium fluoride powder is 1 +/-0.2 mu m.
The preparation method comprises the following steps: (1) Mixing 2 parts of trichloromethane and 28 parts of magnesium fluoride powder, placing the mixture into a high-speed mixer, and fully stirring and mixing for 2-5 minutes to prepare slurry; (2) Mixing 20 parts of PCL pure material and magnesium fluoride powder slurry according to corresponding parts to prepare side feeding material; (3) Extruding the side feeding material and 20 parts of pure PCL material into a melt through a side feeding system of a double-screw extruder, wherein the processing temperature is 135 ℃; (4) After the melt is extruded by the extruder, further kneading and uniformly mixing the melt by adopting an integrated kneading internal mixer, uniformly distributing the magnesium alloy micro powder in the melt, and then granulating to obtain composite master batches; (5) And drying the composite master batch, blending the dried composite master batch with 25 parts of pure PCL (polycaprolactone), and extruding the mixture by using a single screw to obtain the composite 3D printing wire rod, wherein the processing temperature is 135 ℃.
The total content of PCL in the wire rod is 65%, the test shows that the wire rod is smooth, the diameter is 1.75 +/-0.02 mm, the texture is similar to that of an inorganic material, the printing effect is good, and the actual measurement yield of a printed product is more than 95%.
The resulting material was 3D printed as standard splines and tested for tensile properties (GB [0031] T1040.2-2006), flexural strength (GB/T1446-2006) and impact properties (GB/T1943-2008), respectively, with the test results shown in Table 1.
Example 3:
the polycaprolactone magnesium titanate composite 3D printing wire comprises the following components in parts by mass: 95% of PCL, 4% of magnesium titanate powder and 1% of dimethylformamide.
The particle size range of the magnesium titanate powder is 100 +/-10 mu m.
The preparation method comprises the following steps: (1) Blending 2 parts of dimethylformamide and 28 parts of magnesium titanate powder, placing the mixture into a high-speed mixer, and fully stirring and mixing for 2-5 minutes to prepare slurry; (2) Mixing 30 parts of PCL pure material and magnesium titanate powder slurry according to corresponding parts to prepare side feeding material; (3) Extruding the side feeding material and 30 parts of pure PCL material into a melt through a side feeding system of a double-screw extruder, wherein the processing temperature is 135 ℃; (4) After the melt is extruded by the extruder, further kneading and uniformly mixing the melt by adopting an integrated kneading internal mixer, uniformly distributing the magnesium alloy micro powder in the melt, and then granulating to obtain composite master batches; (5) And drying the composite master batch, blending the dried composite master batch with 35 parts of pure PCL material, and extruding the mixture by a single screw to obtain the composite 3D printing wire rod, wherein the processing temperature is 135 ℃.
The total content of PCL in the wire rod is 95%, tests show that the wire rod is smooth, the diameter of the wire rod is 1.75 +/-0.02 mm, the texture of the wire rod is similar to that of an inorganic material, the printing effect is good, and the actual measurement yield of a printed product is more than 95%.
The resulting material was 3D printed as standard splines and tested for tensile properties (GB [0031] T1040.2-2006), flexural strength (GB/T1446-2006) and impact properties (GB/T1943-2008), respectively, with the test results shown in Table 1.
Example 4:
the polycaprolactone calcium magnesium silicate composite 3D printing wire comprises the following components in parts by mass: 80% of PCL, 15% of calcium magnesium silicate powder and 5% of tetrahydrofuran.
The particle size of the calcium magnesium silicate powder is 20 +/-2 mu m.
The preparation method comprises the following steps: (1) Mixing 5 parts of tetrahydrofuran and 15 parts of calcium magnesium silicate powder, placing the mixture into a high-speed mixer, and fully stirring and mixing for 2-5 minutes to prepare slurry; (2) Mixing 25 parts of PCL pure material and calcium magnesium silicate powder slurry according to corresponding parts to prepare side feeding material; (3) Extruding the side feeding material and 25 parts of pure PCL material into a melt through a side feeding system of a double-screw extruder, wherein the processing temperature is 135 ℃; (4) After the melt is extruded by the extruder, further kneading and uniformly mixing the melt by adopting an integrated kneading internal mixer, uniformly distributing the magnesium alloy micro powder in the melt, and then granulating to obtain composite master batches; (5) And drying the composite master batch, blending the dried composite master batch with 30 parts of pure PCL material, and extruding the mixture by using a single screw to obtain the composite 3D printing wire rod, wherein the processing temperature is 135 ℃.
The total content of PCL in the wire rod is 80%, tests show that the wire rod is smooth, the diameter of the wire rod is 1.75 +/-0.02 mm, the texture of the wire rod is similar to that of an inorganic material, the printing effect is good, and the actual measurement yield of a printed product is more than 95%.
The obtained material was printed in 3D form as a standard sample strip, and subjected to tensile property test (GB [0031] -T1040.2-2006), bending strength (GB/T1446-2006) and impact property test (GB/T1943-2008), respectively, and the test results are shown in Table 1.
Comparative example 1: in comparison, all the performances of the 3D printing wire prepared from the pure PCL material are inferior to those of the scheme of the present invention, the pure PCL 3D printing wire is prepared by using the same single screw extrusion process as the above examples and at a processing temperature of 135 ℃, and the comparison of all the performance indexes is shown in table 1.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
TABLE 1 Performance test results of polycaprolactone magnesium ceramic composite material
Claims (8)
1. The utility model provides a compound 3D of polycaprolactone magnesium pottery prints wire rod which characterized in that: the composite material comprises the following components in parts by mass: 65-95% of PCL pure material, 4-30% of magnesium ceramic powder and 0.1-5% of good solvent of polycaprolactone.
2. The PCL magnesium ceramic composite 3D printing wire of claim 1, wherein: the magnesium ceramic is one or more of magnesium oxide, magnesium fluoride, magnesium titanate, magnesium hydroxide, basic magnesium carbonate, calcium magnesium silicate and calcium magnesium carbonate, and the powder particle size range of the magnesium ceramic is 0.2-500 mu m.
3. A preparation method of a PCL magnesium ceramic composite 3D printing wire is characterized by comprising the following steps: the method comprises the following steps:
(1) Respectively weighing the following components in parts by mass: 65% -95% of PCL pure material, 4% -30% of magnesium ceramic powder and 0.1% -5% of good polycaprolactone solvent, wherein the PCL pure material is divided into three parts;
(2) Adding a good solvent of polycaprolactone into the magnesium ceramic powder, and mixing and stirring to prepare slurry;
(3) Mixing the first part of PCL pure material with the magnesium ceramic powder slurry obtained in the step (2), and then feeding the mixture into a side feeding system of a double-screw extruder, and feeding the second part of PCL pure material into a main feeding system of the double-screw extruder to extrude a melt;
(4) After the melt is extruded by the extruder, further kneading and uniformly mixing the melt by adopting an integrated kneading internal mixer, uniformly distributing the magnesium alloy micro powder in the melt, and then granulating to obtain composite master batches;
(5) And drying the composite master batch, blending the dried composite master batch with a third part of pure PCL, and extruding by using a single screw to obtain the PCL-magnesium ceramic composite 3D printing wire.
4. The method of claim 3, wherein: the good solvent of the polycaprolactone used in the step (2) is one or more of polar solvents such as toluene, tetrahydrofuran, ethyl acetate, dichloromethane, trichloromethane, dimethyl sulfoxide, dimethylformamide, hexafluoroisopropanol and the like.
5. The method of claim 3, wherein: the concrete process of preparing the slurry in the step (2) is as follows: putting the raw materials into a high-speed mixer, and fully stirring and mixing for 2-5 min.
6. The method of claim 3, wherein: the double-screw extrusion processing temperature in the step (3) is 80-135 ℃.
7. The method of claim 3, wherein: the single screw extrusion processing temperature in the step (5) is 80-135 ℃.
8. The method of claim 3, wherein: the PCL pure material is added at three parts of a main feed of the double-screw extruder, a side feed of the double-screw extruder and a main feed of the single-screw extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211742023.0A CN115895218A (en) | 2022-12-30 | 2022-12-30 | Polycaprolactone magnesium ceramic composite 3D printing wire and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211742023.0A CN115895218A (en) | 2022-12-30 | 2022-12-30 | Polycaprolactone magnesium ceramic composite 3D printing wire and preparation method thereof |
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| CN103980682A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing polycaprolactone material and preparation method thereof |
| CN104163634A (en) * | 2014-07-02 | 2014-11-26 | 中国电子科技集团公司第五十五研究所 | A thermoplastic material used for three-dimensional printing and an application method thereof |
| CN105665697A (en) * | 2016-03-11 | 2016-06-15 | 中山大学惠州研究院 | Metal or ceramic consumable item for FDM 3D printing, preparation method for metal or ceramic consumable item and finished product printing method |
| CN105934322A (en) * | 2013-12-23 | 2016-09-07 | Omya国际股份公司 | Polymer composition by continuous filler slurry extrusion |
| CN110028335A (en) * | 2019-04-23 | 2019-07-19 | 中国人民解放军总医院 | A kind of method of 3D printing porous ceramics organizational project product |
| CN111554971A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
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| CN105934322A (en) * | 2013-12-23 | 2016-09-07 | Omya国际股份公司 | Polymer composition by continuous filler slurry extrusion |
| CN103980682A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing polycaprolactone material and preparation method thereof |
| CN104163634A (en) * | 2014-07-02 | 2014-11-26 | 中国电子科技集团公司第五十五研究所 | A thermoplastic material used for three-dimensional printing and an application method thereof |
| CN105665697A (en) * | 2016-03-11 | 2016-06-15 | 中山大学惠州研究院 | Metal or ceramic consumable item for FDM 3D printing, preparation method for metal or ceramic consumable item and finished product printing method |
| CN110028335A (en) * | 2019-04-23 | 2019-07-19 | 中国人民解放军总医院 | A kind of method of 3D printing porous ceramics organizational project product |
| CN111554971A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
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