Polymeric based and surface treated metallic hybrid materials and fabrication methods thereof

Abstract

Novel hybrid materials and fabrication methods thereof are provided. The novel hybrid materials can include a biodegradable polymer and a biodegradable metallic material. The hybrid material can also include a coupling agent between the biodegradable metallic material and the biodegradable polymer. A method of fabricating a hybrid material can include performing a surface treatment process on the biodegradable metallic material, and then either performing a solvent formation method or a thermal formation method.

1 . A hybrid material, comprising:
 a biodegradable polymer;   a surface-treated biodegradable metallic material; and   a silane coupling agent chemically bonded to the surface-treated biodegradable metallic material and the biodegradable polymer.   
     
     
         2 . The hybrid material according to  claim 1 , wherein the biodegradable polymer is polycaprolactone, or a copolymer of ε-caprolactone (ε-CL) and γ-butyrolactone (γ-BL), δ-valerolactone (δ-VL), γ-valerolactone (γ-VL), γ-caprolactone (γ-CL), or any combination thereof. 
     
     
         3 . The hybrid material according to  claim 1 , wherein the surface-treated biodegradable metallic material comprises magnesium, magnesium alloy, or both. 
     
     
         4 . The hybrid material according to  claim 1 , wherein the surface-treated biodegradable metallic material comprises magnesium beads with a size of from about 100 nm to about 150 μm. 
     
     
         5 . The hybrid material according to  claim 1 , wherein the silane coupling agent is 3-(trimethoxysilyl)propylmethacrylate or 3-aminopropyltrimethoxysilane. 
     
     
         6 . A method of fabricating a hybrid material comprising a biodegradable polymer and a biodegradable metallic material, wherein the method comprises:
 performing a surface treatment process on the biodegradable metallic material;   dissolving the biodegradable polymer in an organic solvent to form a solution;   adding the biodegradable metallic material, after the surface treatment process has been performed, to the solution;   sonicating the solution;   drying the solution to obtain a pre-hybrid material; and   performing a heat treatment process on the pre-hybrid material.   
     
     
         7 . The method according to  claim 6 , further comprising performing a coupling agent treatment on the biodegradable metallic material before adding the biodegradable metallic material to the solution; wherein performing the coupling agent treatment comprises:
 adding a silane coupling agent and a catalyst to a second solvent to form a coupling agent solution;   adding the biodegradable metallic material to the coupling agent solution to form a coupling agent solution mixture;   heating the coupling agent solution mixture under reflux with nitrogen; and   heat-treating the biodegradable metallic material in a low-vacuum oven.   
     
     
         8 . The method according to  claim 7 , wherein the silane coupling agent is 3-(trimethoxysilyl)propylmethacrylate or 3-aminopropyltrimethoxysilane. 
     
     
         9 . The method according to  claim 8 , wherein heating the coupling agent solution mixture comprises heating the coupling agent solution mixture at a temperature of from about 80° C. or about 110° C. for a period of time of about 3 hours; and wherein heat-treating the biodegradable metallic material comprises heat-treating the biodegradable metallic material at a temperature of about 80° C. to about 100° C. for a period of time of about 5 hours to about 8 hours at a pressure of about 100 mBar; and wherein the second solvent is cyclohexane or toluene; and wherein the catalyst is propylamine or triethylamine. 
     
     
         10 . The method according to  claim 6 , wherein performing a surface treatment process on the biodegradable metallic material comprises performing a plasma immersion ion implantation and deposition process utilizing:
 a negative high voltage power supply with current of about 1.0 mA, a voltage with a magnitude of about 15 kV, a pulse duration of about 300 μs, and a frequency of about 10 Hz;   and a pulsed filtered cathodic arc source with an arc current of about 0.1 A, an arc voltage with a magnitude of about 92V, a triggering voltage with a magnitude of about 12.6 kV, a coil current of about 2.3 A, a pulse duration of about 250 μs, and a frequency of about 10 Hz.   
     
     
         11 . The method according to  claim 6 , wherein the organic solvent is dichloromethane or trichloromethane; and wherein sonicating the solution comprises sonicating the solution for a period of time of from about 30 minutes to about 1 hour; and wherein drying the solution comprises drying the solution for a period of time of from about 12 hours to about 24 hours; and wherein performing a heat treatment process on the pre-hybrid material comprises performing a heat treatment process on the pre-hybrid material at a temperature of about 80° C. for a period of time of from about 30 minutes to about 1 hour. 
     
     
         12 . The method according to  claim 6 , wherein performing a surface treatment process on the biodegradable metallic material comprises performing a plasma immersion ion implantation process, a plasma immersion ion implantation and deposition process, a magnetron sputtering process, or a thermal treatment process on the biodegradable metallic material. 
     
     
         13 . The method according to  claim 6 , wherein performing a surface treatment process on the biodegradable metallic material comprises performing a plasma immersion ion implantation process with a base pressure of about 7.0×10 −6  Torr, a working voltage of from about 15 kV to about 40 kV, a pulse width of about 30 μs, an implantation time of about 3 hours to about 4 hours, a frequency of about 200 Hz, and a working pressure of from about 5.0×10 −4  Ton to about 6.4×10 −4  Torr. 
     
     
         14 . The method according to  claim 6 , wherein performing a surface treatment process on the biodegradable metallic material comprises performing a thermal treatment process on the biodegradable metallic material at a temperature of about 60° C. to about 100° C., a pressure of about 100 mBar, a humidity of from about 10% to about 20%, and a treatment time of from about 8 hours to about 24 hours. 
     
     
         15 . A method of fabricating a hybrid material comprising a biodegradable polymer and a biodegradable metallic material, wherein the method comprises:
 performing a surface treatment process on the biodegradable metallic material;   melting the biodegradable polymer by a thermal process to obtain a polymer melt;   adding the biodegradable metallic material to the polymer melt to form a pre-hybrid material;   shearing the pre-hybrid material in a first direction and a second direction; and   compressing the pre-hybrid material along a third direction to obtain the hybrid material.   
     
     
         16 . The method according to  claim 15 , further comprising performing a coupling agent treatment on the biodegradable metallic material before adding the biodegradable metallic material to the solution; wherein performing the coupling agent treatment comprises:
 adding a silane coupling agent and a catalyst to a second solvent to form a coupling agent solution;   adding the biodegradable metallic material to the coupling agent solution to form a coupling agent solution mixture;   heating the coupling agent solution mixture under reflux with nitrogen; and   heat-treating the biodegradable metallic material in a low-vacuum oven.   
     
     
         17 . The method according to  claim 16 , wherein the silane coupling agent is 3-(trimethoxysilyl)propylmethacrylate or 3-aminopropyltrimethoxysilane; and wherein heating the coupling agent solution mixture comprises heating the coupling agent solution mixture at a temperature of from about 80° C. or about 110° C. for a period of time of about 3 hours; and wherein heat-treating the biodegradable metallic material comprises heat-treating the biodegradable metallic material at a temperature of about 80° C. to about 100° C. for a period of time of about 5 hours to about 8 hours at a pressure of about 100 mBar; and wherein the second solvent is cyclohexane or toluene; and wherein the catalyst is propylamine or triethylamine. 
     
     
         18 . The method according to  claim 15 , wherein performing a surface treatment process on the biodegradable metallic material comprises performing a plasma immersion ion implantation and deposition process utilizing:
 a negative high voltage power supply with current of about 1.0 mA, a voltage with a magnitude of about 15 kV, a pulse duration of about 300 μs, and a frequency of about 10 Hz;   and a pulsed filtered cathodic arc source with an arc current of about 0.1 A, an arc voltage with a magnitude of about 92V, a triggering voltage with a magnitude of about 12.6 kV, a coil current of about 2.3 A, a pulse duration of about 250 μs, and a frequency of about 10 Hz.   
     
     
         19 . The method according to  claim 15 , wherein performing a surface treatment process on the biodegradable metallic material comprises performing a plasma immersion ion implantation process with a base pressure of about 7.0×10 −6  Ton, a working voltage of from about 15 kV to about 40 kV, a pulse width of about 30 μs, an implantation time of about 3 hours to about 4 hours, a frequency of about 200 Hz, and a working pressure of from about 5.0×10 −4  Torr to about 6.4×10 −4  Torr. 
     
     
         20 . The method according to  claim 15 , wherein performing a surface treatment process on the biodegradable metallic material comprises performing a thermal treatment process on the biodegradable metallic material at a temperature of about 60° C. to about 100° C., a pressure of about 100 mBar, a humidity of from about 10% to about 20%, and a treatment time of from about 8 hours to about 24 hours.