There is the preparation method of the polyethylene terephthalate braided material of antibacterial and short mineralization function coating
Technical field
The present invention relates to the preparation method of surface coating of polyethylene terephthalate braided material, be specifically related to the method that the preparation of a kind of atomic layer deposition method has the polyethylene terephthalate braided material of antibacterial and short mineralization function coating.This method belongs to technical field of biological material, and prepared material can be widely used in tissue repair, pharmaceutical carrier.
Background technology
PET material is widely used in biomaterial, and as artificial blood vessel, artificial ligament, but it does not have biologically active, also has problems with the compatibility of tissue.Such as, when repairing for artificial blood vessel, its surface does not have anticoagulant property, easily causes producing thrombus; When repairing for ligament, its surface can not promote tendon-bone healing, easily causes loosening.Therefore, the successful Application of PET material in biomaterial also need by means of surface treatment means.In order to improve the hydrophily of PET to improve biocompatibility in its body further, usually adopt the methods such as alkaline hydrolysis, enzymolysis, Cement Composite Treated by Plasma, chemical graft, although to improve effect better for hydrophilic, but it is poor with surrounding tissue compatibility in vivo, be unfavorable for that surrounding tissue cells is in its superficial growth.Plasma spray coating, electrostatic atomization, magnetron sputtering, ald, chemical vapour deposition (CVD) etc. are all the means that conventional deposition functional materials improves material surface characteristic.But these methods respectively have pluses and minuses, the surface modification for PET class braided material has certain limitation.The temperature needed during plasma spraying is higher, be more suitable for resistant to elevated temperatures metal material, be not suitable for the surface modification of macromolecular material, and the technology such as electrostatic atomization, chemical vapour deposition (CVD) can only realize the top layer modification of material, the coating process carrying out the degree of depth is difficult to for braiding class material.Technique for atomic layer deposition utilizes metallic precursor and nonmetal precursor are alternately exposed to substrate surface and react, its self-limiting growth mechanism can make individual layer individual layer ground repeated growth, deposition parameter height is controlled, and uniformity is good, accurately can must control growth thickness.When PET braided material is used for technical field of biological material, especially have certain flexible material for artificial blood vessel, artificial ligament etc., the pliability not changing material itself after coating is most important.Therefore, the face coat modification of PET braided material has certain challenge.
Interaction between tissue and biomaterial is used successfully to tissue repair for biomaterial and plays key effect.Due to synthetic material implant after on the one hand because material itself easily causes rejection, on the other hand due to the wound that surgical procedure brings, all can cause a large amount of propagation of inflammatory cell.In addition, for artificial ligament, because it directly contacts with bone, in order to promote the combination of material and bone tissue, material has certain promotion mineralization and will be conducive to the synostosis of material and bone tissue.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides the method that the preparation of a kind of atomic layer deposition method has the polyethylene terephthalate braided material of antibacterial and short mineralization function coating, constructed PET braided material has good antibiotic property and promotes mineralization function, and material can be used for the ligament that contacts with bone or bone tissue reparation.
There is a preparation method for the polyethylene terephthalate braided material of antibacterial and short mineralization function coating, it is characterized in that, comprise the steps:
(1) preparation of polyethylene terephthalate braided material: polyethylene terephthalate (PET) silk thread is woven into latticed, tubulose, rope form or other compound shape materials;
(2) surface treatment of PET braided material: under normal temperature, PET braided material is soaked in successively acetone, ethanol, water ultrasonic cleaning 10 minutes, 20 minutes, 30 minutes removal surface impurities respectively, then the PET braided material after clean is placed in air drying, obtains clean PET braided material;
(3) PET braided material ald zinc oxide: clean PET braided material is placed in atomic layer deposition apparatus, adopt diethyl zinc and water as zinc source and oxygen source respectively, high pure nitrogen is as clean air, growth temperature is 200 DEG C, after carrying out 10-500 circulation, obtain the nano-ZnO deposition that thickness is 2-100nm.
The deposition of zinc oxide PET braided material obtained has following performance, and antibiotic rate reaches 70%-90%, also has significantly short calcium, phosphorus deposition.
Advantage of the present invention is: (1) coating has certain degree of depth, can be deep into PET braided fiber internal layer; (2) PET material after coating has good antibiotic property, and antibiotic rate can reach 70%-90%; (3) PET material after coating has good short mineralization ability, the deposition of visible phosphorus, calcium salt; (4) technique for atomic layer deposition is adopted to carry out coating without the need to doing hydrophily process again to PET material.
Accompanying drawing explanation
The stereoscan photograph (500 ×) of the polyethylene terephthalate braided material that Fig. 1 obtains for embodiment 1;
Fig. 2 obtains by embodiment 1 polyethylene terephthalate braided material and adopts technique for atomic layer deposition to carry out the stereoscan photograph (1000 ×) after Zinc oxide coating;
Fig. 3 obtains by embodiment 1 polyethylene terephthalate braided material and adopts technique for atomic layer deposition to carry out the stereoscan photograph (100000 ×) after Zinc oxide coating;
Fig. 4 obtain by embodiment 1 polyethylene terephthalate braided material coating after in simulated body fluid, soak the stereoscan photograph (20000 ×) after 7 days;
Fig. 5 obtain by embodiment 1 polyethylene terephthalate braided material coating after in simulated body fluid, soak the X-ray energy spectrum figure after 7 days.
Detailed description of the invention
Below by way of specific embodiment, technical scheme of the present invention is further described.Following embodiment further illustrates of the present invention, and do not limit the scope of the invention.
embodiment 1:
(1) preparation of polyethylene terephthalate braided material: polyethylene terephthalate (PET) silk thread is woven into latticed;
(2) surface treatment of PET braided material: under normal temperature, PET braided material is soaked in successively acetone, ethanol, water ultrasonic cleaning 10 minutes, 20 minutes, 30 minutes removal surface impurities respectively, then the PET braided material after clean is placed in air drying, obtains clean PET braided material;
(3) PET braided material ald zinc oxide: clean PET braided material is placed in atomic layer deposition apparatus, adopt diethyl zinc and water as zinc source and oxygen source respectively, high pure nitrogen is as clean air, growth temperature is 200 DEG C, after carrying out 300 circulations, obtain the nano-ZnO deposition that thickness is 60nm.
The deposition of zinc oxide PET braided material obtained has following performance, and antibiotic rate reaches 78%, and the atomic percent soaking calcium, phosphorus, Zn-ef ficiency after 7 days in simulated body fluid is respectively: 4.53%, 3.19%, 2.42%.
embodiment 2:
(1) preparation of polyethylene terephthalate braided material: polyethylene terephthalate (PET) silk thread is woven into latticed;
(2) surface treatment of PET braided material: under normal temperature, PET braided material is soaked in successively acetone, ethanol, water ultrasonic cleaning 10 minutes, 20 minutes, 30 minutes removal surface impurities respectively, then the PET braided material after clean is placed in air drying, obtains clean PET braided material;
(3) PET braided material ald zinc oxide: clean PET braided material is placed in atomic layer deposition apparatus, adopt diethyl zinc and water as zinc source and oxygen source respectively, high pure nitrogen is as clean air, growth temperature is 200 DEG C, after carrying out 500 circulations, obtain the nano-ZnO deposition that thickness is 100nm.
The deposition of zinc oxide PET braided material obtained has following performance, and antibiotic rate reaches 90%, and the atomic percent soaking calcium, phosphorus, Zn-ef ficiency after 7 days in simulated body fluid is respectively: 6.28%, 4.36%, 3.57%.
embodiment 3:
(1) preparation of polyethylene terephthalate braided material: polyethylene terephthalate (PET) silk thread is woven into latticed;
(2) surface treatment of PET braided material: under normal temperature, PET braided material is soaked in successively acetone, ethanol, water ultrasonic cleaning 10 minutes, 20 minutes, 30 minutes removal surface impurities respectively, then the PET braided material after clean is placed in air drying, obtains clean PET braided material;
(3) PET braided material ald zinc oxide: clean PET braided material is placed in atomic layer deposition apparatus, adopt diethyl zinc and water as zinc source and oxygen source respectively, high pure nitrogen is as clean air, growth temperature is 200 DEG C, after carrying out 200 circulations, obtain the nano-ZnO deposition that thickness is 40nm.
The deposition of zinc oxide PET braided material obtained has following performance, and antibiotic rate reaches 70%, and the atomic percent soaking calcium, phosphorus, Zn-ef ficiency after 7 days in simulated body fluid is respectively: 3.21%, 2.58%, 4.27%.
embodiment 4:
(1) preparation of polyethylene terephthalate braided material: polyethylene terephthalate (PET) silk thread is woven into latticed;
(2) surface treatment of PET braided material: under normal temperature, PET braided material is soaked in successively acetone, ethanol, water ultrasonic cleaning 10 minutes, 20 minutes, 30 minutes removal surface impurities respectively, then the PET braided material after clean is placed in air drying, obtains clean PET braided material;
(3) PET braided material ald zinc oxide: clean PET braided material is placed in atomic layer deposition apparatus, adopt diethyl zinc and water as zinc source and oxygen source respectively, high pure nitrogen is as clean air, growth temperature is 200 DEG C, after carrying out 10 circulations, obtain the nano-ZnO deposition that thickness is 2nm.
The deposition of zinc oxide PET braided material obtained has following performance, and antibiotic rate reaches 30%, and the atomic percent soaking calcium, phosphorus, Zn-ef ficiency after 7 days in simulated body fluid is respectively: 1.25%, 0.82%, 4.36%.