High modulus crosslinked polyethylene with reduced residual free radical concentration prepared below the melt

Abstract

The present invention provides an irradiated crosslinked polyethylene containing reduced free radicals, preferably containing substantially no residual free radical. Disclosed is a process of making irradiated crosslinked polyethylene by irradiating the polyethylene in contact with a sensitizing environment at an elevated temperature that is below the melting point, in order to reduce the concentration of residual free radicals to an undetectable level. A process of making irradiated crosslinked polyethylene composition having reduced free radical content, preferably containing substantially no residual free radicals, by mechanically deforming the polyethylene at a temperature that is below the melting point of the polyethylene, optionally in a sensitizing environment, is also disclosed herein.

1 . A method of making a medical prosthesis comprising irradiated crosslinked polyethylene composition, wherein the method comprises the steps of:
 a) irradiating polyethylene at a temperature that is below the melting point of the polyethylene in order to form free radicals that crosslink by recombination; and   b) mechanically deforming the polyethylene from step a) at a temperature that is above room temperature and below the melting point of the irradiated polyethylene in order to mobilize residual free radicals that are trapped to allow residual free radicals to recombine and form additional crosslinks, thereby providing a medical prosthesis having irradiated crosslinked polyethylene composition, wherein molecules of the irradiated crosslinked polyethylene composition are orientated through the mechanical deforming.   
   
   
       2 - 62 . (canceled) 
   
   
       63 . The method of  claim 1 , wherein the mechanical deformation mode is selected from the group consisting of channel flow, uniaxial compression, biaxial compression, oscillatory compression, uniaxial tension, biaxial tension, ultra-sonic oscillation, bending, plane stress compression (channel die), and combinations thereof. 
   
   
       64 . The method of  claim 1 , wherein the polyethylene is mechanically deformed by bending. 
   
   
       65 . The method of  claim 1 , wherein the medical prosthesis is an orthopedic joint or a bone replacement part selected from the group consisting of a hip, a knee, an elbow, or an ankle replacement part. 
   
   
       66 . The method of  claim 1 , wherein the mechanical deformation of the polyethylene is carried out on a machined components. 
   
   
       67 . A method of achieving molecular orientation in an irradiated crosslinked polyethylene composition, wherein the method comprises the steps of:
 a) irradiating polyethylene at a temperature that is above the melting point of the polyethylene in order to form free radicals that crosslink by recombination, thereby forming a crosslinked polyethylene;   b) mechanically deforming the crosslinked polyethylene from step a) at a molten-state in order to mobilize residual free radicals that are trapped to allow residual free radicals to recombine and form additional crosslinks, thereby providing an irradiated crosslinked polyethylene composition, wherein molecules of the irradiated crosslinked polyethylene composition are orientated through the mechanical deforming.   
   
   
       68 . The method of  claim 67 , wherein the mechanical deformation mode is selected from the group consisting of channel flow, uniaxial compression, biaxial compression, oscillatory compression, uniaxial tension, biaxial tension, ultra-sonic oscillation, bending, plane stress compression (channel die), and combinations thereof. 
   
   
       69 . The method of  claim 67 , wherein the polyethylene is mechanically deformed by bending. 
   
   
       70 . The method of  claim 67 , wherein the polyethylene is irradiated at a dose level between about 1 and about 1,000 kGy. 
   
   
       71 . The method of  claim 1 , wherein the mechanical deformation of the polyethylene is carried out on a machined components. 
   
   
       72 . A method of imparting molecular orientation in an irradiated crosslinked polyethylene composition, wherein the method comprises the steps of:
 a) mechanically deforming polyethylene at a solid- or a molten-state, thereby providing a polyethylene composition having molecular orientation; and   b) irradiating the polyethylene of step a) at the deformed state at a temperature that is below the melting point of polyethylene in order to form free radicals that crosslink by recombination, thereby providing an irradiated crosslinked polyethylene composition, wherein molecules of the irradiated crosslinked polyethylene composition are orientated through the mechanical deforming.   
   
   
       73 . The method of  claim 72 , wherein the polyethylene is ultra-high molecular weight polyethylene (UHMWPE). 
   
   
       74 . The method of  claim 72 , wherein the mechanical deformation mode is selected from the group consisting of channel flow, uniaxial compression, biaxial compression, oscillatory compression, uniaxial tension, biaxial tension, ultra-sonic oscillation, bending, plane stress compression (channel die), and combinations thereof. 
   
   
       75 . The method of  claim 72 , wherein the polyethylene is mechanically deformed by bending. 
   
   
       76 . The method of  claim 72 , wherein polyethylene composition is a medical implant. 
   
   
       77 . A method of fabricating a medical implant comprising a crosslinked polymeric material having molecular orientation, wherein the method comprises the steps of:
 a) mechanically deforming the medical implant at a temperature that is below the melting temperature of the polymeric material; and   b) irradiating the medical implant of step a) at the deformed state at a temperature that is below the melting point of the polymeric material in order to form free radicals that crosslink by recombination, thereby providing a medical implant comprising the crosslinked polymeric material, wherein molecules of the crosslinked polymeric material are orientated through the mechanical deforming.   
   
   
       78 . The method of  claim 77 , wherein the mechanical deformation mode is selected from the group consisting of channel flow, uniaxial compression, biaxial compression, oscillatory compression, uniaxial tension, biaxial tension, ultra-sonic oscillation, bending, plane stress compression (channel die), and combinations thereof. 
   
   
       79 . A medical implant made according to the method of  claim 77 . 
   
   
       80 . The medical implant according to  claim 79  is an orthopedic joint or a bone replacement part selected from the group consisting of a hip, a knee, an elbow, or an ankle replacement part. 
   
   
       81 . The medical implant according to  claim 79  is a thin polyethylene tibial knee insert, low conformity articulations, or acetabular liner. 
   
   
       82 . A method of fabricating a medical implant comprising a crosslinked polymeric material having molecular orientation, wherein the method comprises the steps of:
 a) irradiating the medical implant at a temperature that is below the melting point of the polymeric material in order to form free radicals that crosslink by recombination, thereby forming a medical implant having crosslinked polymeric material; and   b) mechanically deforming the medical implant having crosslinked polymeric material from step a) in order to mobilize residual free radicals that are trapped to allow residual free radicals to recombine and form additional crosslinks, thereby providing a medical implant comprising the crosslinked polymeric material, wherein molecules of the crosslinked polymeric material are orientated through the mechanical deforming.   
   
   
       83 . The method of  claim 82 , wherein the mechanical deformation mode is selected from the group consisting of channel flow, uniaxial compression, biaxial compression, oscillatory compression, uniaxial tension, biaxial tension, ultra-sonic oscillation, bending, plane stress compression (channel die), and combinations thereof. 
   
   
       84 . A medical implant made according to the method of  claim 82 . 
   
   
       85 . The medical implant according to  claim 84  is an orthopedic joint or a bone replacement part selected from the group consisting of a hip, a knee, an elbow, or an ankle replacement part. 
   
   
       86 . The medical implant according to  claim 84  is a thin polyethylene tibial knee insert, low conformity articulations, or acetabular liner.