CN103751849A - Ultrahigh molecular weight polyethylene composite material for fusible body processing of artificial joint - Google Patents
Ultrahigh molecular weight polyethylene composite material for fusible body processing of artificial joint Download PDFInfo
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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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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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
- B29C2948/92704—Temperature
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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
- B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
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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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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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
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Abstract
The invention relates to an ultrahigh molecular weight polyethylene composite material for a fusible body processing of artificial joint. The material is prepared by mixing ultrahigh molecular weight polyethylene (UHMWPE) and ultra-low viscosity high-density polyethylene (HDPE), the fusible body processing property of UHMWPE is greatly improved due to addition of the ultra-low viscosity HDPE, the relative content of UHMWPE in UHMWPE/HDPE mixture in the vibration shearing injection molding process can be furthest improved, and the excellent performance of UHMWPE is maintained; furthermore, a great amount of oriental lamella and oriental shish-kebab structures are formed inside the material due to vibration shearing injection molding, the tensile performance, the impact strength and abrasion resistance of the material can be remarkably improved. Compared with a press molded UHMWPE, the material is more applicable to the field of artificial joint implant materials.
Description
Technical field
The invention belongs to field of biomedical polymer materials, relate to a kind of artificial joint melt processible ultra-high molecular weight polyethylene composite material.
Background technology
Ultra-high molecular weight polyethylene (UHMWPE) has excellent mechanical performance, impact resistance, mar proof, fatigue durability and biocompatibility, successfully be applied to artificial joint substitution material field (Kurtz, S.M.et al.Biomaterials1999,20 (18), 1659-1688.).But due to its relative molecular mass high (200～6,000,000 g/mol), melt viscosity is very big, the processing and forming of UHMWPE is a very large difficult problem.Up to the present, the method for processing this biomaterial is mainly confined to compressing and plunger type and extrudes, particularly compressing (Kurtz, S.M.et al.The UHMWPE handbook.AccessOnline via Elsevier:2004).The compressing UHMWPE that requires stops for a long time (more than 200 ℃ under High Temperature High Pressure, at least 2h), high temperature stops the probability that can increase UHMWPE molecular chain rupture for a long time, making material be more prone to oxidation becomes fragile, and, be oxidized remaining free radical in the process that becomes fragile and can cause some immunoreation of patient.In addition, because the diffusivity between UHMWPE strand is very poor, the compressing elimination intergranular interface of its powder preferably that is difficult to, thereby inevitably can make to exist in moulded products some fault of construction (Muratoglu, O.K.et al.Biomaterials1999,20 (16), 1463-1470).These faults of construction can cause product surface to occur crackle, the expansion of crackle can be accelerated again the surface abrasion of joint replacement materials, finally causes the inefficacy in advance of joint material, and, these defects also can become stress concentration point, damage greatly the mechanical property of joint replacement materials.
From compressing different, conventional melt processing, for example twin-screw extrusion and injection mo(u)lding, have high-strength hybrid stress field, can make macromolecular material plasticizing forming within relatively low temperature and relatively short time, avoid these shortcomings of having mentioned above.But conventional melt processing request polymer has lower melt viscosity.UHMWPE obviously reaches less than this requirement, therefore can not adopt these conventional melt processing method molding.In order to address this problem, can be by adding exterior lubricant (Smith, P.; Lemstra.et al.Journal of Materials Science1980; 15 (2); 505-514); or by macromolecule less to itself and some viscosity; as the blend such as polypropylene, Polyethylene Glycol realize (Lee; E.M et al.Polymers for Advanced Technologies2009,20 (12), 1121-1126; Xie, M.et al.European polymer journal2007,43 (8), 3480-3487.).But these methods can be brought the poor and poor problem of interface compatibility of biocompatibility.
It should be noted that; high density polyethylene (HDPE) (HDPE) has and the identical chemical constitution of UHMWPE and crystal structure; there is good biocompatibility simultaneously; therefore (Xu in the work in early stage; L.et al.ACS applied materials & interfaces2012; 4 (3), 1521-1529; Huang, Y.-F.et al.J.Mater.Chem.B2013, DOI:10.1039/C3TB21231A), we can improve UHMWPE and HDPE blend the processing characteristics of UHMWPE, under can the prerequisite of oscillatory shear injection mo(u)lding, the percetage by weight of UHMWPE is the highest can only reach 40%～50%.So the UHMWPE of low content can not give full play to itself excellent properties, as mar proof.Therefore, we should improve the relative amount of UHMWPE in UHMWPE/HDPE blend as far as possible, and still, this will inevitably bring the problem that is difficult to melt processing.
Summary of the invention
The object of the invention is to obtain the UHMWPE relative amount high composite of trying one's best in UHMWPE/HDPE composite, to maintain the excellent properties of UHMWPE itself, guarantee the melt processible of UHMWPE/HDPE simultaneously; In inside, form a large amount of orientation platelets and shish-kebab (shish-kebab) structure, there is excellent mechanical property, impact property and abrasion resistance properties.
The present invention is as follows for realizing the technical scheme of above-mentioned purpose:
A ultra-high molecular weight polyethylene composite material for melt processible for artificial joint, described UHMWPE accounts for 40%～90% of described UHMWPE/HDPE blend mass percent.
Described ultra-high molecular weight polyethylene composite material adopts following steps to prepare:
(1) HDPE modified materials preparation: the HDPE mechanical mixture of the ultra-low viscosity that the UHMWPE that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 130～140 ℃ to stir 80～100 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is 3～4 times of solution, making to contain the UHMWPE/HDPE blend that UHMWPE mass percent is 2% separates out, then filter, by leaching thing, at 100 ℃, be dried to below water content not higher than 0.01% of own wt, finally obtain HDPE modified materials;
(2) UHMWPE and the preparation of HDPE modified materials blend: by after UHMWPE and step (1) gained HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, then this blending extrudant is forced to cooling and pelletizing, and be dried to water content not higher than 0.01% of own wt at 100 ℃.Wherein, the conveying compression section of described extruder, melt zone and metering section temperature are set as respectively 210～230 ℃, 230～250 ℃ and 230～240 ℃, and engine speed is set as 120～140 revs/min, and charging rate is 5～7 revs/min;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding.The barrel temperature of described oscillatory shear injection moulding machine is 230～240 ℃, and nozzle temperature is 240～250 ℃, and hot flow path Temperature Setting is 250～270 ℃, and mold temperature is 18～40 ℃.
The mark of material used is weight portion above.
Preferably, described UHMWPE is biological medical grade, and its relative molecular mass is 500～6,000,000 grams/mol, and UHMWPE powder diameter is 100～400 μ m; Described HDPE is biological medical grade, and its melt flow rate (MFR) is greater than 45g/10min (0.325kg, 190 ℃).
In above-mentioned steps (2), preferably, described UHMWPE shared mass percent in UHMWPE/HDPE blend is 40%～90%, the combination property optimum during wherein containing UHMWPE90%.Than compressing pure UHMWPE, the tensile property of the UHMWPE composite of described melt processible, impact strength and mar proof are all significantly improved.
The present invention compared with prior art, has following remarkable advantage:
(1) the present invention selects HDPE and the UHMWPE blend that a kind of viscosity pole is low, when UHMWPE relative amount is increased to 90%, still has good melt processability.Thereby make this UHMWPE composite can adopt conventional extruding and injection mo(u)lding, improved greatly working (machining) efficiency, avoided the problem of low, the difficult elimination of fusion defects of compressing efficiency of present stage.
(2) the UHMWPE composite of the melt processible of preparing by the present invention is to adopt Vibration Injection Molding molding.Oscillatory shear injection mo(u)lding, compared with common injection mo(u)lding, can provide lasting shear stress field at packing stage, thereby impels the inside of melt processible UHMWPE composite in the course of processing to form a large amount of orientation platelets and shish-kebab structure.These structures make Vibration Injection Molding UHMWPE composite compared with compressing pure UHMWPE, have the mechanical performance of significantly improving.Particularly, impact strength and ultimate tensile strength are respectively from 29.6 ± 1.3kJ/m
2be increased to 90.6 ± 1.6kJ/m with 30.8 ± 1.4MPa
2with 65.5 ± 3.1MPa, increase rate is respectively 206.1% and 112.7%.
(3) the UHMWPE material of the melt processible of preparing by the present invention, has farthest retained the combination property of UHMWPE excellence, and for example, rate of depreciation is down to 7.1mg/MC from 10.0mg/MC.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram sheet of the compressing pure UHMWPE sample of comparative example 1 of the present invention;
Fig. 2 is the scanning electron microscope diagram sheet of the embodiment of the present invention 1 oscillatory shear injection mo(u)lding sample orientation platelet;
Fig. 3 is the scanning electron microscope diagram sheet of the embodiment of the present invention 1 oscillatory shear injection mo(u)lding sample orientation shish-kebab;
Fig. 4 is the scanning electron microscope diagram sheet of the embodiment of the present invention 2 oscillatory shear injection mo(u)lding sample orientation platelets;
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are just for being further detailed the present invention; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to foregoing invention content, still belong to protection scope of the present invention.
In addition, it is pointed out that the material in following examples is weight portion.
Embodiment 1
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE powder that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 140 ℃ to stir 100 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 3 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 90%UHMWPE and 10%HDPE mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 230 ℃, 250 ℃ and 240 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 134 revs/min, charging rate is 6 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 240 ℃ and 250 ℃, and hot flow path Temperature Setting is 270 ℃, and mold temperature is set as 20 ℃.
Embodiment 2
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 138 ℃ to stir 90 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 4 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 80%UHMWPE powder and 20%HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 220 ℃, 240 ℃ and 230 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 140 revs/min, charging rate is 5 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 230 ℃ and 240 ℃, and hot flow path Temperature Setting is 260 ℃, and mold temperature is set as 22 ℃.
Embodiment 3
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE powder that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 135 ℃ to stir 80 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 3 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 70%UHMWPE powder and 30%HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 225 ℃, 230 ℃ and 235 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 138 revs/min, charging rate is 6 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 235 ℃ and 245 ℃, and hot flow path Temperature Setting is 260 ℃, and mold temperature is set as 30 ℃.
Embodiment 4
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE powder that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 120 ℃ to stir 100 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 4 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 60%UHMWPE powder and 40%HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 230 ℃, 245 ℃ and 240 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 145 revs/min, charging rate is 7 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 237 ℃ and 240 ℃, and hot flow path Temperature Setting is 255 ℃, and mold temperature is set as 27 ℃.
Embodiment 4
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE powder that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 120 ℃ to stir 100 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 4 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 60%UHMWPE powder and 40%HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 230 ℃, 245 ℃ and 240 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 145 revs/min, charging rate is 7 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 237 ℃ and 240 ℃, and hot flow path Temperature Setting is 255 ℃, and mold temperature is set as 27 ℃.
Embodiment 5
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE powder that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 128 ℃ to stir 85 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 3 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 50%UHMWPE powder and 50%HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 210 ℃, 235 ℃ and 235 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 140 revs/min, charging rate is 6 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 230 ℃ and 240 ℃, and hot flow path Temperature Setting is 250 ℃, and mold temperature is set as 20 ℃.
Embodiment 6
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE powder that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 135 ℃ to stir 90 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 3 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 40%UHMWPE powder and 60%HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 210 ℃, 230 ℃ and 230 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 138 revs/min, charging rate is 5 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 230 ℃ and 240 ℃, and hot flow path Temperature Setting is 250 ℃, and mold temperature is set as 40 ℃.
Comparative example 1
The component proportion providing by comparative example in table one 1 carries out material compression molding molding at 200 ℃, and clamp time is 2.0h, prepares pure UHMWPE pressing for Performance Ratio.
Comparative example 2
The component proportion providing by comparative example in table one 2 carries out material compression molding molding at 200 ℃, and clamp time is 2.0h, and preparation 90%UHMWPE/10%UHDPE pressing for Performance Ratio
Comparative example 3
(1) HDPE modified materials preparation: the HDPE mechanical mixture that the UHMWPE powder that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 130 ℃ to stir 100 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is solution 4 times, the UHMWPE/HDPE blend that to make containing UHMWPE mass percent be 2% is separated out, and then filters, will leach thing 100 ℃ dry 12 hours;
(2) UHMWPE and the preparation of modification HDPE blend: by after 30%UHMWPE powder and 70%HDPE modified materials mechanical mixture, being placed in double screw extruder melt blending extrudes, it is 210 ℃, 235 ℃ and 230 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, engine speed is set as 120 revs/min, charging rate is 5 revs/min, then this blend is forced to cooling and pelletizing, and at 100 ℃, be dried to water content not higher than 0.01% of own wt;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding, and injecting machine material tube and nozzle temperature are set as respectively 230 ℃ and 235 ℃, and hot flow path Temperature Setting is 250 ℃, and mold temperature is set as 30 ℃.
The present invention is also to comparative example 1, and the microscopic pattern of embodiment 1 and embodiment 2 adopts scanning electron microscope to observe, and the results are shown in accompanying drawing 1-4.What accompanying drawing 1 represented is the scanning electron microscope diagram of comparative example 1, and can observing sample, inner what generate is the platelet of a large amount of random.What accompanying drawing 2-4 represented is to add after the ultra-low viscosity HDPE of different quality mark, during with Vibration Injection Molding molding, the scanning electron microscope diagram of corresponding sample, can find out, under Oscillatory shear field action, in sample, formed the platelet and shish-kebab (shish-kebab) structure that along field of flow direction, are orientated in a large number, this is the immanent cause that material property is improved.
For mechanical property, impact strength and the abrasion resistance properties of artificial joint melt processible UHMWPE material prepared by the present invention are assessed, utilize ASTM-D638 to carry out tensile property test, GB/T1843-96 carries out impact property test, GB/T3960-83 carries out polishing machine test, and test result is in Table two.By with ultra-low viscosity HDPE blend, guaranteeing under the prerequisite of Vibration Injection Molding success molding, the relative amount of UHMWPE in UHMWPE/HDPE blend be from 40%～50% of previous work, is the highlyest increased to 90%.This material has excellent combination property, and the more compressing pure UHMWPE of its hot strength and impact strength has improved respectively 206.1% and 112.7%, and rate of depreciation drops to 7.1mg/MC from 10.0mg/MC.Therefore, the present invention proposes a kind of method that can significantly improve UHMWPE processability, make this material can be by conventional hot plastic processing method molding, and, the UHMWPE composite of melt processible prepared by the method has excellent combination property, can be used for artificial joint material field.
The formula of table one embodiment 1-6 and comparative example 1-3
| Embodiment | UHMWPE relative amount (weight) | HDPE relative amount (weight) |
| 1 | 90% | 10% |
| 2 | 80% | 20% |
| 3 | 70% | 30% |
| 4 | 60% | 40% |
| 5 | 50% | 50% |
| 6 | 40% | 60% |
| Comparative example 1 | 100% | 0% |
| Comparative example 2 | 90% | 10% |
| Comparative example 3 | 30% | 70% |
[0065]the tensile property of table two embodiment 1-6 and comparative example 1-3, impact property and abrasion resistance properties comparison
| Embodiment | Hot strength (MPa) | Impact property (kJ/m 2） | Rate of depreciation (mg/MC) |
| 1 | 65.5 | 90.6 | 7.1 |
| 2 | 61.5 | 94.3 | 7.7 |
| 3 | 58.4 | 72.4 | 8.1 |
| 4 | 50.5 | 62.0 | 8.5 |
| 5 | 48.7 | 55.9 | 8.9 |
| 6 | 46.8 | 50.0 | 9.1 |
| Comparative example 1 | 30.8 | 29.6 | 10.0 |
| Comparative example 2 | 27.8 | 25.3 | 10.5 |
| Comparative example 3 | 43.3 | 46.7 | 9.6 |
Claims (5)
1. a ultra-high molecular weight polyethylene composite material for melt processible for artificial joint, is characterized in that, described UHMWPE accounts for 40%～90% of described UHMWPE/HDPE blend mass percent.
2. the ultra-high molecular weight polyethylene composite material of melt processible for artificial joint according to claim 1, is characterized in that, the mass fraction that UHMWPE accounts for UHMWPE/HDPE blend is 90%.
3. the ultra-high molecular weight polyethylene composite material of melt processible for artificial joint according to claim 1, is characterized in that, described ultra-high molecular weight polyethylene composite material adopts following steps to prepare:
(1) HDPE modified materials preparation: the HDPE mechanical mixture of the ultra-low viscosity that the UHMWPE that is 2% by mass percent and mass percent are 98%, add xylene solution blend until form homogeneous phase transparent solution, then it is continued at 130～140 ℃ to stir 80～100 minutes; Gained solution is injected in the ethanol of room temperature, ethanol volume is 3～4 times of solution, making to contain the UHMWPE/HDPE blend that UHMWPE mass percent is 2% separates out, then filter, by leaching thing, at 100 ℃, be dried to below water content not higher than 0.01% of own wt, finally obtain HDPE modified materials;
(2) UHMWPE and the preparation of HDPE modified materials blend: by after UHMWPE and step (1) gained HDPE modified materials mechanical mixture; being placed in double screw extruder melt blending extrudes; then this blending extrudant is forced to cooling and pelletizing, and be dried to water content not higher than 0.01% of own wt at 100 ℃; Wherein, the conveying compression section of described extruder, melt zone and metering section temperature are set as respectively 210～230 ℃, 230～250 ℃ and 230～240 ℃, and engine speed is set as 120～140 revs/min, and charging rate is 5～7 revs/min;
(3) oscillatory shear injection mo(u)lding: the above-mentioned dried pellet of extruding is carried out to oscillatory shear injection mo(u)lding; The barrel temperature of described oscillatory shear injection moulding machine is 230～240 ℃, and nozzle temperature is 240～250 ℃, and hot flow path Temperature Setting is 250～270 ℃, and mold temperature is 18～40 ℃.
4. the ultra-high molecular weight polyethylene composite material of melt processible for artificial joint according to claim 3, it is characterized in that, wherein ultra-low viscosity HDPE used is the bio-medical level that melt flow rate (MFR) is greater than 45g/10min, and UHMWPE used is that molecular weight is the bio-medical level of 500～6,000,000 grams/mol.
5. the ultra-high molecular weight polyethylene composite material of melt processible for artificial joint according to claim 3, is characterized in that, the UHMWPE in described step (2) accounts for described UHMWPE/HDPE blend quality mass fraction 90%; In double screw extruder, melt blending is extruded, and it is 230 ℃, 250 ℃ and 240 ℃ that extruder is carried compression section, melt zone and metering section Temperature Setting, and engine speed is set as 134 revs/min, and charging rate is 6 revs/min; In described (3) oscillatory shear injection mo(u)lding: injecting machine material tube and nozzle temperature are set as respectively 240 ℃ and 250 ℃, and hot flow path Temperature Setting is 270 ℃, and mold temperature is set as 20 ℃.
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