CN103980595B - Modified ultrahigh molecular polyethylene for 3D printing and preparation method thereof - Google Patents
Modified ultrahigh molecular polyethylene for 3D printing and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2207/066—LDPE (radical process)
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Abstract
A modified ultrahigh molecular polyethylene material for 3D printing comprises the following components, by weight, 80-95 parts of ultrahigh molecular polyethylene, 30-40 parts of low-density polyethylene, 10-15 parts of carbon nanotube, 1-10 parts of an inorganic filling material, 1-5 parts of a modifier, 0.1-0.5 part of an antioxidant and 0.1-0.5 part of a coupling agent. The modified UHMWPE material provided by the invention has good melt fluidity, heat resistance and abrasion resistance. By the preparation method, the ultrahigh molecular polyethylene is more in line with characteristics of a 3D printing material, and the ultrahigh molecular polyethylene has a wide application prospect in the 3D printing technology.
Description
Technical field
The present invention relates to a kind of modified ultra-high molecular weight polyethylene material and preparation method thereof, be specifically related to a kind of modified ultra-high molecular weight polyethylene material for 3D printing and preparation method thereof.
Background technology
3D printing technique mainly comprises the techniques such as SLA, FDM, SLS, LOM.Wherein fused glass pellet technology (FDM) and selective laser sintering (SLS) technology all use thermoplastics as basic 3D printed material.
As the thermoplastic engineering plastic that a kind of molecular weight with linear structure is high, the molecular structure of ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is substantially identical with common polythene material.But UHMWPE has the performance such as shock-resistant, wear-resistant, self lubricity, resistance to chemical attack of the unrivaled excellence of other plastics because molecular weight is high.And UHMWPE resistance to low temperature is excellent, still has higher shock strength, even can use at-269 DEG C-40 DEG C time.The Physical Mechanical of UHMWPE excellence makes it can be widely used in the fields such as machinery, transport, weaving, papermaking, mining industry, building, military affairs, agricultural, chemical industry and sports movement apparatus, being most widely used wherein with heavy packages container and pipeline.In addition, due to the physiological inertia of UHMWPE excellence, it uses in clinical medicine as heart valve, orthopedics's part, joint prosthesis etc.
Although UHMWPE has the characteristic of many excellences, also there are many deficiencies.UHMWPE has high molecular weight, and its molecular chain is very long, and extremely long molecular chain mutually entanglement can cause its melt to be elastomeric high viscosity elastomerics, and mobility is very poor, and easily shear fracture phenomenon occurs.Melt flow rate (MFR) (MFR) low (almost nil), fusing point high (190-210 DEG C), viscosity greatly, extremely difficult machine-shaping etc.In addition compared with Other Engineering plastics, have that surface hardness is low, heat-drawn wire is low, flexural strength and the shortcoming such as creep resistant is poor, antiwear property is poor, intensity is low, thus make the forming process of UHMWPE become very difficult, seriously hamper its application, make it not satisfactory as 3D printed material.
CN1433443A relates to a kind of method that formation embeds the complex body of nanofiber in the polymer matrix, the method is included in plastic substrate and is mixed into nanofiber to form coacervate, and the nanofiber that distributes equably under being in hydrodynamic force stress by diplomatic corps's aggressiveness; Described hydrodynamic force stress makes described coacervate split off, and can be used to realize minor diameter and arrangement in conjunction with carrying out extra extension flowing.Gained complex body can deposit (FDM) with consolidation shaping, wherein the polymkeric substance that a volume nanofiber strengthens is used as the wire raw material of FDM technique.In this process, nanofiber complex line (diameter is about 2 millimeters) is extruded through the die head of mm size, produces complex line in a row and makes sheet material and 3D parts.Raw material used in this patent is the polymkeric substance wire rod that nanofiber strengthens.Its shortcoming is: the FDM of nanofiber complex line is very complicated, not easily processes.
CN1812878A relates to a kind of powder being suitable for 3D printing, and this powder comprises the blend of thermoplastic granulates thing and adhesive particle thing, and wherein said thermoplastic granulates thing is optional from polyolefine.The powder of this patent, when printing for 3D, needs to use solvent.Therefore, it is liquid composition that the 3D of CN1812878A prints system, and its shortcoming is to need to use in many cases to solvent or the dispersion agent of the mankind and bad environmental, and complicated operation, not easily dispersed or dissolve.
CN102093646A relates to a kind of material for 3D printing rapid shaping and preparation method thereof, rapid prototyping material comprises modified powder materials A and binding agent B, wherein: the preparation of modified powder materials A: powdered material and the first solvent are joined ball mill or grinding machine for grinding, powdered material pre-treatment material is obtained; By tensio-active agent, lubricant, organic resin successively joins in the second solvent, and dispersed with stirring 2-3h, obtains modification liquid; Powdered material pre-treatment material is mixed with modification liquid, puts into shredder, normal temperature mixed grinding, dry, grind, obtain modified powder materials A; During use, 1 part of modified powder materials A and 0.01-0.07 part binding agent B adapted.This patent 3D formed body used is solution system, and its shortcoming is to need to grind and modification material in preparation materials process, and uses supercritical drying, complicated operation.
US2004/0232583A1 relates to a kind of method manufacturing three-dimensional body, and it comprises: a) provide a powdered substrate layer; B) on one or more regions of described base material, selectivity applies microwave-absorbing first sensitive materials of at least one; C) layer described in microwave radiation processing is used at least one times.Wherein loosely mention the polymkeric substance that can use and be selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, PMMI, PMMA, ionomer, polymeric amide, copolyesters, copolyamide, terpolymer, ABS or its mixture.US2004/0232583A1 does not mention and carries out modification to polyethylene, is suitable for 3D printing to make it.
US3,847,888 relate to a kind of ultrahigh molecular weight linear polyethylene, and its molecular weight is at least 1 × 10
6, density is 0.92-0.99.Its not mentioned described ultrahigh molecular weight linear polyethylene application in 3D printed material.
Prior art is all not mentioned carries out modification to make to be suitable for 3D printing to ultrahigh molecular weight polyethylene(UHMWPE).Therefore, the object of the invention is at present its melt flow rate (MFR) is low, viscosity large, poor fluidity and the extremely feature such as difficulty injection moulding process machine-shaping, propose a kind of method improving the fluidity of molten of UHMWPE material.By adding the fluidity of molten to improve material such as appropriate Low Density Polyethylene, flow ability modifying agent, coupling agent and mineral filler, improve its mechanical property such as thermotolerance, wearability simultaneously.The MFR value of the material of gained is greater than 2g/10min (experimental technique carries out according to GB/T3682-2000 (ISO1133)) by almost nil bringing up to, and makes it be suitable for use as 3D printed material.
Summary of the invention
The present invention relates to a kind of modified ultra-high molecular weight polyethylene material printed for 3D, it comprises following component by weight, is preferably made up of following component:
The commercially available acquisition of described ultrahigh molecular weight polyethylene(UHMWPE), its molecular weight can be greater than 1,500,000, and be such as 150-300 ten thousand, density is at 0.93-0.96g/cm
3between, heat-drawn wire is 85-90 DEG C.The consumption of described ultrahigh molecular weight polyethylene(UHMWPE) is preferably 82-92 part, is more preferably 85-90 part.
Described Low Density Polyethylene is the polyethylene that high pressure polymerisation produces, and its commercially available acquisition, its density is generally 0.93-0.95g/cm
3, melt index is generally 2.0-2.10g/10min.The consumption of described Low Density Polyethylene is preferably 30-38 part, is more preferably 30-35 part.
Described carbon nanotube can be various carbon nanotube, such as Single Walled Carbon Nanotube, multi-walled carbon nano-tubes.The present inventor finds surprisingly, activates described carbon nanotube with ordinary method nitric acid, and nitric acid activation energy makes its specific surface area greatly increase, and can improve avtive spot, improves dispersiveness in the base.The concrete technology of nitric acid activation can be carbon nanotube backflow 2h-2.5h in concentrated nitric acid (65%), carries out disperseing (such as stirring, ultrasonic disperse, preferred ultrasonic disperse) simultaneously, is then washed till neutrality with distilled water.The consumption of described carbon nanotube is preferably 10-14 part, is more preferably 10-13 part.
Described mineral filler is selected from molybdenumdisulphide, glass microballon, talcum powder, super-fine silicon micro-powder.Preferably, described molybdenumdisulphide is the molybdenum disulfide particles with 1000-1500 order granularity.Preferably, described glass microballon for having 10-50 micron granularity, the glass microballon of 1-2 micron wall thickness.Preferably, described talcum powder fineness is not less than is 5000 object talcum powder.Preferably, the particle diameter of described super-fine silicon micro-powder is 0.1-0.3 micron.The consumption of described mineral filler is preferably 1-8 part, is more preferably 1-5 part.
Described properties-correcting agent is selected from polyester or poly-(methyl) acrylate.Described polyester is such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN (PEN) or PBN (PBN).Described poly-(methyl) acrylate can be poly-(methyl) methyl acrylate, poly-(methyl) ethyl propenoate, poly-(methyl) propyl acrylate, poly-(methyl) butyl acrylate, poly-(methyl) cyclohexyl acrylate etc.The consumption of described properties-correcting agent is preferably 1-4 part, is more preferably 1-3 part.
In preferred embodiments, modified ultra-high molecular weight polyethylene material of the present invention is also containing oxidation inhibitor.Preferably, described oxidation inhibitor is antioxidant CA.Its consumption is 0.1-0.5 part, is preferably 0.1-0.4 part.
In another preferred embodiment of the present, modified ultra-high molecular weight polyethylene material of the present invention is also containing coupling agent.Described coupling agent is selected from titanic acid ester, silane.Titanic acid ester can be sec.-propyl three (isostearoyl base) titanic acid ester, sec.-propyl three (dioctyl pyrophosphate) titanic acid ester or two (dioctyl pyrophosphoryl bases) containing fluoroacetic acid ester titanium, is preferably sec.-propyl three (isostearoyl base) titanic acid ester.Described silane is preferably KH-550 type silane coupling agent.Selected coupling agent can reduce the viscosity of molten synthetic resin, improves the dispersity of weighting agent to improve processing characteristics, and then makes goods obtain good surface quality and machinery, heat and electrical property.The consumption of described coupling agent is 0.1-0.5 part, is preferably 0.1-0.4 part.
In one aspect of the invention, the purposes of modified ultra-high molecular weight polyethylene material of the present invention in 3D prints also is related to.
In another aspect of this invention, also relate to a kind of 3D Method of printing, it is characterized in that using modified ultra-high molecular weight polyethylene material of the present invention.
The invention still further relates to a kind of method preparing the modified ultra-high molecular weight polyethylene material for 3D printing of the present invention, it is characterized in that each component extruding pelletization.
The present inventor finds surprisingly, if first the solution of mineral filler with properties-correcting agent and coupling agent is mixed, then the mixture of gained is mixed with other components of matrix material of the present invention after the drying, and by the mixture extruding pelletization of gained, obtain thus and there is homodisperse matrix material, and the matrix material of gained has excellent melt flow rate (MFR), be very suitable for 3D and print.
More specifically, described method has following processing step:
1) be dispersed in dispersion medium by mineral filler, then add properties-correcting agent and coupling agent, dispersion is also dry;
2) by supramolecule weight northylen, Low Density Polyethylene, carbon nanotube, in step 1) in obtain mineral filler and oxidation inhibitor mixing;
3) will in step 2) in the extruding pelletization that obtains, thus obtain modified ultra-high molecular weight polyethylene material.
In step 1) in, before being dispersed in dispersion medium, preferably that mineral filler is dry.Step 1) in dispersion medium used can be ethanol, water, acetone, be preferably ethanol.Described dispersion can be undertaken by stirring, ultrasonic disperse, is preferably undertaken by ultrasonic disperse.
In step 2) in, described mixing can be carried out in high-speed mixer.
Step 3) in extruding pelletization single screw extrusion machine or twin screw extruder can be used to carry out.When using twin screw extruder, procession parameters is: opening for feed is followed successively by 230-240,240-250,250-260,250-260,240-250,240-250 DEG C to machine barrel each section of temperature distribution of mouth mould, and engine speed is 300-350r/min.
In preferred embodiments, the invention still further relates to a kind of method preparing the modified ultra-high molecular weight polyethylene material for 3D printing of the present invention, it is characterized in that described method comprises following processing step:
1) first that mineral filler is dry, be dispersed in dispersion medium, stir, under agitation add properties-correcting agent and coupling agent in proportion, then stir.Then vibrating dispersion in ultra-sonic oscillation instrument, dries to constant weight.
2) by supramolecule weight northylen, Low Density Polyethylene, carbon nanotube, in step 1) in the mineral filler of gained, properties-correcting agent and coupling agent mixture, oxidation inhibitor mixes in proportion in high-speed mixer.
3) by step 2) middle extruding pelletization, thus obtain modified UHMWPE.
Preferably, the preparation technology of described modified ultra-high molecular weight polyethylene material is as follows:
1) first by mineral filler at 160 DEG C dry 4 hours, be dispersed in after weighing in ethanol medium, stir 30 minutes to evenly by electric blender, properties-correcting agent, coupling agent are added in dispersion medium in proportion, then stir 30 minutes to evenly.Then, in ultra-sonic oscillation instrument, vibrating dispersion, after 1 hour, is dried to constant weight, for subsequent use.
2) by supramolecule weight northylen, Low Density Polyethylene, carbon nanotube, step 1) in obtain mineral filler, oxidation inhibitor, join in high-speed mixer and mix.
3) by step 2) in mix after material add extruding pelletization in twin screw extruder and make modified UHMWPE pellet.Procession parameters: opening for feed is to machine barrel each section of temperature distribution 230-240 of mouth mould, 240-250,250-260,250-260,240-250,240-250 DEG C, and engine speed is 300r/min.
In order to test, also the pellet that step 3 obtains is injection molded into standard test specimen through injection moulding machine.Molding proces s parameters: barrel zone temperature is followed successively by 200-210,210-220,220-230,230-240,240-250,245-255 DEG C from opening for feed to the machine barrel of mouth mould each section of temperature distribution; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The feature that the present invention gives prominence to is:
1. modified UHMWPE material of the present invention has good fluidity of molten (>2g/10min), thus makes to be very suitable for 3D printing.
2. modified UHMWPE material of the present invention has high heat resistance, wearability.
3. production cost of the present invention is low, and production process is simple, is easy to suitability for industrialized production.
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 embodiment.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.
Unless otherwise stated, the present invention's " part " used and percentage ratio are all based on weight.
MFR test performs according to GSB15-1312-2012, the test of cantilever beam impact strength, Izod notched impact strength performs according to GB1043-79, tensile strength performs according to GBT1040-2006, elongation at break test performs according to ISO6239, heat-drawn wire test performs according to GB/T1633-2000, and PVvalue testing performs according to GB10006-1988.In Examples below, carbon nanotube used is the carbon nanotube with nitric acid activation, and concrete technology is as follows: by carbon nanotube backflow 2h in concentrated nitric acid (65%), carry out ultrasonic disperse simultaneously, be then washed till neutrality with distilled water.
Embodiment 1
1) first by molybdenumdisulphide at 160 DEG C dry 4 hours; be dispersed in after weighing in ethanol medium; 30 minutes are stirred to even by electric blender; 5 parts of properties-correcting agent polymethylmethacrylates, 0.2 part of coupling agent sec.-propyl three (isostearoyl base) titanic acid ester are added in dispersion medium, then stirs 30 minutes to even.Then, in ultra-sonic oscillation instrument, vibrating dispersion, after 1 hour, is dried to constant weight, for subsequent use.
2) by the UHMWPE of 95 weight parts, 30 parts of Low Density Polyethylenes, the carbon nanotube of 10 parts, the molybdenumdisulphide of 5 parts, the antioxidant CA of 0.1 part and in step 1) in the product of gained join in high-speed mixer and mix, discharging after abundant mixed grinding reaction 1h.
3) by step 2) in the compound that obtains to add length-to-diameter ratio be that in the twin screw extruder of 36, extruding pelletization makes UHMWPE pellet.The time that material stops in an extruder is 3 minutes.Extruder temperature is set as successively: opening for feed is to machine barrel each section of temperature distribution 230,240,250,250,240,240 DEG C of mouth mould, and engine speed is 300r/min.
4) by step 3) in the pellet that obtains be injection molded into standard test specimen through injection moulding machine.Molding proces s parameters: opening for feed is 200,210,220,230,240,245 DEG C to machine barrel each section of temperature distribution of mouth mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of pure UHMWPE and modified UHMWPE-1 detected, its detected result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-1 |
| MFR/(10min) -1 | 0 | 2.54 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 90 |
| Izod notched impact strength/kJm -2 | 10 | 70 |
| Tensile strength/MPa | 34 | 22 |
| Elongation at break/% | 350 | 380 |
| Heat-drawn wire/DEG C | 85 | 80 |
| Frictional coefficient | 0.07 | 0.32 |
Embodiment 2
1) UHMWPE of 90 weight parts, 35 parts of Low Density Polyethylenes, the carbon nanotube of 10 parts, the talcum powder of 10 parts, the polymethylmethacrylate of 2 parts, the antioxidant CA of 0.5 part, 0.5 part of sec.-propyl three (isostearoyl base) titanic acid ester are joined in high-speed mixer and mix, discharging after abundant mixed grinding reaction 1h.
2) by step 1) in the compound that obtains to add length-to-diameter ratio be that in the twin screw extruder of 36, extruding pelletization makes UHMWPE pellet.The time that material stops in an extruder is 5 minutes.Extruder temperature is set as successively: opening for feed is 235,245,250,255,240,240 DEG C to machine barrel each section of temperature distribution of mouth mould, and engine speed is 300r/min.
3) pellet that step 3 obtains is injection molded into standard test specimen through injection moulding machine.Molding proces s parameters: opening for feed is 205,215,220,235,240,250 DEG C to machine barrel each section of temperature distribution of mouth mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of pure UHMWPE and modified UHMWPE-2 detected, its detected result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-2 |
| MFR/(10min) -1 | 0 | 2.04 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 88 |
| Izod notched impact strength/kJm -2 | 10 | 62 |
| Tensile strength/MPa | 34 | 22 |
| Elongation at break/% | 350 | 410 |
| Heat-drawn wire/DEG C | 85 | 83.2 |
| Frictional coefficient | 0.09 | 0.25 |
Embodiment 3
1) UHMWPE of 95 weight parts, 40 parts of Low Density Polyethylenes, the carbon nanotube of 15 parts, 10 parts of glass microballons, 3 parts of polymethylmethacrylates, 0.5 part of antioxidant CA, 0.5 part of silane are joined in high-speed mixer and mix, discharging after abundant mixed grinding reaction 1h.
2) by step 1) in the compound that obtains to add length-to-diameter ratio be that in the twin screw extruder of 36, extruding pelletization makes UHMWPE pellet.The time that material stops in an extruder is 5 minutes.Extruder temperature is set as successively: opening for feed is 240,250,260,260,250,250 DEG C to machine barrel each section of temperature distribution of mouth mould, and engine speed is 300r/min.
3) pellet that step 3 obtains is injection molded into standard test specimen through injection moulding machine.Molding proces s parameters: opening for feed is 210,220,230,240,250,255 DEG C to machine barrel each section of temperature distribution of mouth mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of pure UHMWPE and modified UHMWPE-3 is detected, its inspection
Result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-3 |
| MFR/(10min) -1 | 0 | 2.45 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 92 |
| Izod notched impact strength/kJm -2 | 10 | 67 |
| Tensile strength/MPa | 34 | 24 |
| Elongation at break/% | 350 | 385 |
| Heat-drawn wire/DEG C | 85 | 80 |
| Frictional coefficient | 0.10 | 0.28 |
Embodiment 4
1) UHMWPE of 80 weight parts, 40 parts of Low Density Polyethylenes, the carbon nanotube of 15 parts, the silicon powder of 10 parts, poly-(methyl) ethyl propenoate of 5 parts, the antioxidant CA of 0.3 part, silane of 0.1 part are joined in high-speed mixer and mix, discharging after abundant mixed grinding reaction 1h.
2) by step 1) in the compound that obtains to add length-to-diameter ratio be that in the twin screw extruder of 36, extruding pelletization makes UHMWPE pellet.The time that material stops in an extruder is 3 minutes.Extruder temperature is set as successively: opening for feed is 235,250,255,260,250,250 DEG C to machine barrel each section of temperature distribution of mouth mould, and engine speed is 300r/min.
3) pellet that step 3 obtains is injection molded into standard test specimen through injection moulding machine.Molding proces s parameters: opening for feed is 200,215,230,235,240,255 DEG C to machine barrel each section of temperature distribution of mouth mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of pure UHMWPE and modified UHMWPE-4 is detected, its inspection
Result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-4 |
| MFR/(10min) -1 | 0 | 3.36 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 98 |
| Izod notched impact strength/kJm -2 | 10 | 69 |
| Tensile strength/MPa | 34 | 24 |
| Elongation at break/% | 350 | 421 |
| Heat-drawn wire/DEG C | 85 | 74 |
| Frictional coefficient | 0.10 | 0.26 |
As seen from the above embodiment, by adding the fluidity of molten that appropriate Low Density Polyethylene, flow ability modifying agent, coupling agent and mineral filler etc. improve to a great extent, improve its mechanical property such as thermotolerance, wearability simultaneously, make it be suitable for use as 3D printed material.
Claims (14)
1. the purposes of modified ultra-high molecular weight polyethylene material in 3D prints, is characterized in that described modified ultra-high molecular weight polyethylene material comprises following component by weight:
2. purposes according to claim 1, is characterized in that described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
3. purposes according to claim 1, is characterized in that described carbon nanotube nitric acid activates.
4. purposes according to claim 1, is characterized in that described mineral filler is selected from molybdenumdisulphide, glass microballon, talcum powder or super-fine silicon micro-powder.
5. purposes according to claim 1, is characterized in that described properties-correcting agent is selected from polyester or poly-(methyl) acrylate.
6. purposes according to claim 1, is characterized in that described modified ultra-high molecular weight polyethylene material also containing oxidation inhibitor.
7. purposes according to claim 1, is characterized in that described modified ultra-high molecular weight polyethylene material also containing coupling agent.
8. a 3D Method of printing, is characterized in that using modified ultra-high molecular weight polyethylene material, it is characterized in that described modified ultra-high molecular weight polyethylene material comprises following component by weight:
9. method according to claim 8, is characterized in that described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
10. method according to claim 8, is characterized in that described carbon nanotube nitric acid activates.
11. methods according to claim 8, is characterized in that described mineral filler is selected from molybdenumdisulphide, glass microballon, talcum powder or super-fine silicon micro-powder.
12. methods according to claim 8, is characterized in that described properties-correcting agent is selected from polyester or poly-(methyl) acrylate.
13. methods according to claim 8, is characterized in that described modified ultra-high molecular weight polyethylene material also containing oxidation inhibitor.
14. methods according to claim 8, is characterized in that described modified ultra-high molecular weight polyethylene material also containing coupling agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356618B (en) * | 2014-10-29 | 2016-01-06 | 衢州学院 | A kind of biomass wood plastic composite for 3D printing and preparation method thereof |
| CN105622803B (en) * | 2014-11-17 | 2018-08-24 | 中国科学院化学研究所 | A kind of new application of random hyperbranched polyethylene |
| CN104761761B (en) * | 2015-03-28 | 2016-08-24 | 武汉纺织大学 | The nanofiber of a kind of high tenacity strengthens rubber-based 3D printing material and preparation method |
| CN105099348B (en) * | 2015-09-01 | 2017-11-14 | 南通友邦金塑制品有限公司 | A kind of support meanss of photovoltaic panel support beam |
| CN105288751B (en) * | 2015-11-06 | 2018-04-03 | 中国矿业大学 | A kind of multi-gradient bionic joint cartilage material preparation process based on 3D printing |
| CN106832513A (en) * | 2016-12-30 | 2017-06-13 | 洛阳国润新材料科技股份有限公司 | A kind of ultrahigh molecular weight polyethylene tubing and preparation method thereof |
| US11661521B2 (en) | 2019-12-17 | 2023-05-30 | Ticona Llc | Three-dimensional printing system employing a thermotropic liquid crystalline polymer |
| CN111440371A (en) * | 2020-03-24 | 2020-07-24 | 杭州联通管业有限公司 | Anti-freezing polyethylene power tube and preparation method thereof |
| EP4201994A1 (en) * | 2020-08-18 | 2023-06-28 | Mitsui Chemicals, Inc. | Ethylene-based polymer composition and use application thereof |
| CN114213810A (en) * | 2021-12-28 | 2022-03-22 | 宁波美佳速创智能科技有限公司 | High-strength 3D printing photosensitive resin material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1937763A2 (en) * | 2005-08-08 | 2008-07-02 | Cabot Corporation | Polymeric compositions containing nanotubes |
| WO2010035851A1 (en) * | 2008-09-24 | 2010-04-01 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Resin composition |
| CN102438798A (en) * | 2009-04-08 | 2012-05-02 | 纳米技术股份有限公司 | Continuous method assisted by ultrasound with a variable amplitude and frequency for the preparation of nanocompoundds based on polymers and nanoparticles |
| EP2448383A1 (en) * | 2010-10-26 | 2012-05-02 | Politecnico di Torino | Process for producing conductive and/or piezoresistive traces on a polymeric substrate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8299159B2 (en) * | 2009-08-17 | 2012-10-30 | Laird Technologies, Inc. | Highly thermally-conductive moldable thermoplastic composites and compositions |
-
2014
- 2014-04-30 CN CN201410183492.2A patent/CN103980595B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1937763A2 (en) * | 2005-08-08 | 2008-07-02 | Cabot Corporation | Polymeric compositions containing nanotubes |
| WO2010035851A1 (en) * | 2008-09-24 | 2010-04-01 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Resin composition |
| CN102438798A (en) * | 2009-04-08 | 2012-05-02 | 纳米技术股份有限公司 | Continuous method assisted by ultrasound with a variable amplitude and frequency for the preparation of nanocompoundds based on polymers and nanoparticles |
| EP2448383A1 (en) * | 2010-10-26 | 2012-05-02 | Politecnico di Torino | Process for producing conductive and/or piezoresistive traces on a polymeric substrate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020169423A1 (en) * | 2019-02-20 | 2020-08-27 | Basell Polyolefine Gmbh | Extrusion additive manufacturing process for producing polyethylene articles |
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