CN106086838B - Neodymium zinc-cobalt alloy/polypropylene timbering material preparation method - Google Patents

Neodymium zinc-cobalt alloy/polypropylene timbering material preparation method Download PDF

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CN106086838B
CN106086838B CN201610445688.3A CN201610445688A CN106086838B CN 106086838 B CN106086838 B CN 106086838B CN 201610445688 A CN201610445688 A CN 201610445688A CN 106086838 B CN106086838 B CN 106086838B
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polypropylene
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neodymium
zinc
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CN106086838A (en
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蓝碧健
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Taicang Biqi New Material Research Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/60—Materials for use in artificial skin
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/22—Materials or treatment for tissue regeneration for reconstruction of hollow organs, e.g. bladder, esophagus, urether, uterus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/32—Materials or treatment for tissue regeneration for nerve reconstruction

Abstract

The invention belongs to biomedical material technologies, are related to a kind of preparation method of neodymium zinc-cobalt alloy/polypropylene timbering material.The preparation method of the timbering material includes that polypropylene timbering material cleans, surface is modified, catalytic activation and chemical plating neodymium zinc-cobalt alloy.The advantages of preparation method of the present invention is: the organic carbon flood rate of timbering material reduces by 99% or more, and Mohs' hardness can reach 6.3, and through 180 days simulated body fluid corrosion tests, metal ion flood rate was less than 1ppm, i.e. the material has high biotic environment reliability.Neodymium zinc-cobalt alloy/polypropylene material can be used for tissue engineering bracket material, and application prospect is bright and clear, and market potential is huge.

Description

Neodymium zinc-cobalt alloy/polypropylene timbering material preparation method
Technical field
The invention belongs to biomedical material technologies, are related to a kind of system of neodymium zinc-cobalt alloy/polypropylene timbering material Preparation Method.
Background technique
Bio-medical material is for replacing, repairing living tissue natural or artificial material.Bio-medical material and extension Human longevity and improve the quality of living closely bound up, thus technical field of biological material is increasingly taken seriously.In recent years, materialogy and The progress of biology is that the development of bio-medical material is laid a good foundation.And adding with population in the world aging process Speed, the mankind are to health and long-lived pursuit, the increasing of athletic injury, the increase of difficult patient and the patient for needing to replace tissue Phenomena such as age reduces all proposes very big demand to biomaterial.Currently, not only implant surgery increases, repairing after implantation Multiple operation is consequently increased.Prosthesis causes pain to patient, and cost high success rate is low, this just mentions biomaterial Higher requirement is gone out.
Polypropylene for medical article is a kind of plastics as obtained by propylene polymerization.It can be subjected to high pressure steam sterilization, there is good power Learn performance and chemical stability and physiology drop property.Mainly for the manufacture of medical catheter, infusion vessel, flat artificial kidney folder The films such as plate, packaging material, syringe are handled through surfactant, become hydrophilic porous film, can artificial lung processed.Fiber is used as The blood of bubble oxygenator defoams filter screen, stomach wall patch, sutures etc..
In Medical rack material, metallic support density is big, and it is big to retain human body burden in vivo；Polymer support density is small, Human body burden is small, but polymer is degradable, generates " organic carbon " and overflows, unfavorable to human body；Metal/polymer composite material type branch Frame can be in conjunction with the advantages of the two, but the type of metal is limited, expensive mostly based on noble metal gold, silver, platinum etc..The present invention To be coated with neodymium zinc-cobalt alloy layer in polypropylene surface, core process be under the activation of ferrimanganic composite catalyzing, it is molten in chemical plating In liquid, rear earth element nd enters in the lattice of zinc-cobalt alloy, more form compact and stable alloy-layer is formed, so effectively by poly- third Alkene is isolated with human body, reduces polypropylene organic carbon flood rate by 99% or more, moreover, neodymium zinc-cobalt alloy/polypropylene bracket The Mohs' hardness of material can reach 6.3, be best in current all metals/polypropylene composite materials timbering material；It was simulated through 180 days Human body fluid corrosion test, neodymium zinc-cobalt alloy/polypropylene timbering material metal ion flood rate is less than hundred a ten thousandths (1ppm) illustrates that the material has high biotic environment reliability.In conclusion neodymium zinc-cobalt alloy proposed by the present invention/poly- The preparation method of propylene timbering material has substantive distinguishing features outstanding and significant progress, that is, has creativeness.
Summary of the invention
The invention belongs to biomedical material technologies, are related to a kind of system of neodymium zinc-cobalt alloy/polypropylene timbering material Preparation Method.The step of preparation method, is as follows:
1) successively use weight percent concentration water-soluble for 10% hydrazine hydrate aqueous solution, 5% dioxygen on polypropylene bracket Liquid, deionized water are cleaned, are dried；
2) clean polypropylene branch is placed in modifier solution 30 minutes, takes out, is placed in baking oven in 100 DEG C of dryings It 3 hours, is cooled to room temperature, obtains modified polypropene bracket；It is deionized water that wherein the formula of modifier solution, which is solvent, in solution Various solute concentrations are respectively as follows: 3-aminopropyltriethoxysilane 3~6g/L of concentration, and cyanacrylate concentration 9~ 12g/L, cyclohexanone peroxide 1~3g/L of concentration, 100~200g/L of acetone concentration.
3) modified polypropene branch is placed in activator solution 30 minutes, takes out, is washed with deionized water, dried, then It is placed in the sodium borohydride aqueous solution that weight percent concentration is 3% 10 minutes, takes out, clean, polypropylene bracket must be activated；Its The formula of middle activator solution is that solvent is deionized water, in solution various solute concentrations be respectively as follows: ferrous nitrate concentration 20~ 30g/L, manganese nitrate 20~30g/L of concentration, 20~30g/L of sodium citrate concentration.
4) will activation polypropylene branch be placed in neodymium zinc cobalt electroless plating solution, in 75 DEG C chemical plating 3 hours, take out clean, Drying, obtains neodymium zinc-cobalt alloy/polypropylene timbering material.It is deionized water that wherein the formula of neodymium zinc cobalt electroless plating solution, which is solvent, Various solute concentrations are respectively as follows: 20~30g/L of neodymium nitrate concentration in solution；20~30g/L of nitric acid cobalt concentration；Nitric acid zinc concentration 40 ~60g/L；30~60g/L of phosphate dihydrogen sodium concentration；60~90g/L of sodium citrate concentration；3~6g/ of dimethylamino borane concentration L；6~9g/L of ammonium sulfate concentrations.
5) neodymium zinc-cobalt alloy/polypropylene timbering material test characterization.Neodymium zinc-cobalt alloy/polypropylene timbering material is placed in mould In quasi- human body fluid, place 180 days, take out in 37 DEG C, test organic carbon spill-out in solution, and with polypropylene timbering material phase Compare, calculates organic carbon and overflow reduced rate；With the constituent content of Energy Dispersive X-ray detector (EDX) test bracket material, meter Calculate the flood rate of neodymium, zinc, cobalt ions；With the bending modulus of universal testing machine test bracket material, measured with Mohs' hardness Try the surface hardness of timbering material.Wherein each component content of simulated body fluid: NaCl 8g/L, KCl 0.4g/L, NaHCO3 0.35g/L, CaCl20.14g/L, Na2HPO40.06g/L, KH2PO40.06g/L, MgSO4.7H2O 0.2g/L, glucose 1g/L。
It can be used for tissue engineering bracket material with neodymium zinc-cobalt alloy/polypropylene timbering material prepared by preparation method of the invention Material includes: bone, cartilage, blood vessel, nerve, skin and artificial organs, such as the tissue stent material of liver,spleen,kidney, bladder.
Specific embodiment
The invention is further illustrated by the following examples
Embodiment 1
By polypropylene bracket successively use weight percent concentration be 10% hydrazine hydrate aqueous solution, 5% hydrogen peroxide solution, Deionized water is cleaned, is dried.
By 3.6g 3-aminopropyltriethoxysilane, 9g cyanacrylate, 2.7g cyclohexanone peroxide is dissolved in In 168g acetone, deionized water is added, is made into the modifier solution that volume is 1L.
Clean polypropylene branch is placed in modifier solution 30 minutes, is taken out, is placed in baking oven in 100 DEG C dry 3 Hour, it is cooled to room temperature, obtains modified polypropene bracket.
By 29g ferrous nitrate, 21g manganese nitrate, 25g sodium citrate is dissolved in 500mL deionized water, then is diluted to volume and is The activator solution of 1L.
Modified polypropene branch is placed in activator solution 30 minutes, takes out, is washed with deionized water, is dried, then set It 10 minutes in the sodium borohydride aqueous solution that weight percent concentration is 3%, takes out, cleans, polypropylene bracket must be activated.
By 24g neodymium nitrate, 23g cobalt nitrate, 49g zinc nitrate, 57g sodium dihydrogen phosphate, 75g sodium citrate, 4g dimethylamino Borine, 9g ammonium sulfate are dissolved in 500mL deionized water, then are diluted to the neodymium zinc cobalt electroless plating solution that volume is 1L.
Will activation polypropylene branch be placed in neodymium zinc cobalt electroless plating solution, in 75 DEG C chemical plating 3 hours, take out clean, dry It is dry, obtain neodymium zinc-cobalt alloy/polypropylene timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose are dissolved in 500mL deionized water, then are diluted to the simulated body fluid that volume is 1L.
Neodymium zinc-cobalt alloy/polypropylene timbering material is placed in simulated body fluid, is placed 180 days in 37 DEG C, is taken out, is surveyed Organic carbon spill-out in solution is tried, and compared with polypropylene timbering material, calculating organic carbon to overflow reduced rate is 99.4%；With The constituent content of Energy Dispersive X-ray detector (EDX) test bracket material, calculate neodymium, zinc, cobalt ions flood rate be respectively 0.7ppm,0.6ppm,0.8ppm；Bending modulus with universal testing machine test bracket material is 1.09GPa, hard with Mohs The surface hardness of degree measurement examination timbering material is 7.9.
Embodiment 2
By polypropylene bracket successively use weight percent concentration be 10% hydrazine hydrate aqueous solution, 5% hydrogen peroxide solution, Deionized water is cleaned, is dried.
By 6g 3-aminopropyltriethoxysilane, 12g cyanacrylate, 3g cyclohexanone peroxide is dissolved in 200g In acetone, deionized water is added, is made into the modifier solution that volume is 1L.
Clean polypropylene branch is placed in modifier solution 30 minutes, is taken out, is placed in baking oven in 100 DEG C dry 3 Hour, it is cooled to room temperature, obtains modified polypropene bracket.
By 30g ferrous nitrate, 30g manganese nitrate, 30g sodium citrate is dissolved in 500mL deionized water, then is diluted to volume and is The activator solution of 1L.
Modified polypropene branch is placed in activator solution 30 minutes, takes out, is washed with deionized water, is dried, then set It 10 minutes in the sodium borohydride aqueous solution that weight percent concentration is 3%, takes out, cleans, polypropylene bracket must be activated.
By 30g neodymium nitrate, 30g cobalt nitrate, 60g zinc nitrate, 60g sodium dihydrogen phosphate, 90g sodium citrate, 6g dimethylamino Borine, 9g ammonium sulfate are dissolved in 500mL deionized water, then are diluted to the neodymium zinc cobalt electroless plating solution that volume is 1L.
Will activation polypropylene branch be placed in neodymium zinc cobalt electroless plating solution, in 75 DEG C chemical plating 3 hours, take out clean, dry It is dry, obtain neodymium zinc-cobalt alloy/polypropylene timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose are dissolved in 500mL deionized water, then are diluted to the simulated body fluid that volume is 1L.
Neodymium zinc-cobalt alloy/polypropylene timbering material is placed in simulated body fluid, is placed 180 days in 37 DEG C, is taken out, is surveyed Organic carbon spill-out in solution is tried, and compared with polypropylene timbering material, calculating organic carbon to overflow reduced rate is 99.7%；With The constituent content of Energy Dispersive X-ray detector (EDX) test bracket material, calculate neodymium, zinc, cobalt ions flood rate be respectively 0.27ppm,0.46ppm,0.61ppm；Bending modulus with universal testing machine test bracket material is 1.33GPa, with not The surface hardness of family name's hardometer test bracket material is 6.8.
Embodiment 3
By polypropylene bracket successively use weight percent concentration be 10% hydrazine hydrate aqueous solution, 5% hydrogen peroxide solution, Deionized water is cleaned, is dried.
By 4.4g 3-aminopropyltriethoxysilane, 11.2g cyanacrylate, 2.1g cyclohexanone peroxide is molten In 155g acetone, deionized water is added, is made into the modifier solution that volume is 1L.
Clean polypropylene branch is placed in modifier solution 30 minutes, is taken out, is placed in baking oven in 100 DEG C dry 3 Hour, it is cooled to room temperature, obtains modified polypropene bracket.
By 22.6g ferrous nitrate, 27.3g manganese nitrate, 26.7g sodium citrate is dissolved in 500mL deionized water, then is diluted to Volume is the activator solution of 1L.
Modified polypropene branch is placed in activator solution 30 minutes, takes out, is washed with deionized water, is dried, then set It 10 minutes in the sodium borohydride aqueous solution that weight percent concentration is 3%, takes out, cleans, polypropylene bracket must be activated.
By 21.8g neodymium nitrate, 22.9g cobalt nitrate, 53.4g zinc nitrate, 51.2g sodium dihydrogen phosphate, 88.6g sodium citrate, 4.4g dimethylamino borine, 6.8g ammonium sulfate are dissolved in 500mL deionized water, then are diluted to the neodymium zinc cobalt electroless plating that volume is 1L Solution.
Will activation polypropylene branch be placed in neodymium zinc cobalt electroless plating solution, in 75 DEG C chemical plating 3 hours, take out clean, dry It is dry, obtain neodymium zinc-cobalt alloy/polypropylene timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose are dissolved in 500mL deionized water, then are diluted to the simulated body fluid that volume is 1L.
Neodymium zinc-cobalt alloy/polypropylene timbering material is placed in simulated body fluid, is placed 180 days in 37 DEG C, is taken out, is surveyed Organic carbon spill-out in solution is tried, and compared with polypropylene timbering material, calculating organic carbon to overflow reduced rate is 99.7%；With The constituent content of Energy Dispersive X-ray detector (EDX) test bracket material, calculate neodymium, zinc, cobalt ions flood rate be respectively 0.33ppm,0.36ppm,0.38ppm；Bending modulus with universal testing machine test bracket material is 1.11GPa, with not The surface hardness of family name's hardometer test bracket material is 6.6.
Embodiment 4
By polypropylene bracket successively use weight percent concentration be 10% hydrazine hydrate aqueous solution, 5% hydrogen peroxide solution, Deionized water is cleaned, is dried.
By 3.2g 3-aminopropyltriethoxysilane, 11.5g cyanacrylate, 2.6g cyclohexanone peroxide is molten In 163g acetone, deionized water is added, is made into the modifier solution that volume is 1L.
Clean polypropylene branch is placed in modifier solution 30 minutes, is taken out, is placed in baking oven in 100 DEG C dry 3 Hour, it is cooled to room temperature, obtains modified polypropene bracket.
By 28.1g ferrous nitrate, 23.4g manganese nitrate, 26.1g sodium citrate is dissolved in 500mL deionized water, then is diluted to Volume is the activator solution of 1L.
Modified polypropene branch is placed in activator solution 30 minutes, takes out, is washed with deionized water, is dried, then set It 10 minutes in the sodium borohydride aqueous solution that weight percent concentration is 3%, takes out, cleans, polypropylene bracket must be activated.
By 23.8g neodymium nitrate, 26.9g cobalt nitrate, 42.1g zinc nitrate, 56.7g sodium dihydrogen phosphate, 77.6g sodium citrate, 5.1g dimethylamino borine, 7.8g ammonium sulfate are dissolved in 500mL deionized water, then are diluted to the neodymium zinc cobalt electroless plating that volume is 1L Solution.
Will activation polypropylene branch be placed in neodymium zinc cobalt electroless plating solution, in 75 DEG C chemical plating 3 hours, take out clean, dry It is dry, obtain neodymium zinc-cobalt alloy/polypropylene timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose are dissolved in 500mL deionized water, then are diluted to the simulated body fluid that volume is 1L.
Neodymium zinc-cobalt alloy/polypropylene timbering material is placed in simulated body fluid, is placed 180 days in 37 DEG C, is taken out, is surveyed Organic carbon spill-out in solution is tried, and compared with polypropylene timbering material, calculating organic carbon to overflow reduced rate is 99.0%；With The constituent content of Energy Dispersive X-ray detector (EDX) test bracket material, calculate neodymium, zinc, cobalt ions flood rate be respectively 0.22ppm,0.34ppm,0.54ppm；Bending modulus with universal testing machine test bracket material is 1.01GPa, with not The surface hardness of family name's hardometer test bracket material is 6.8.
Embodiment 5
By polypropylene bracket successively use weight percent concentration be 10% hydrazine hydrate aqueous solution, 5% hydrogen peroxide solution, Deionized water is cleaned, is dried.
By 3g 3-aminopropyltriethoxysilane, 9g cyanacrylate, 1g cyclohexanone peroxide is dissolved in 100g third In ketone, deionized water is added, is made into the modifier solution that volume is 1L.
Clean polypropylene branch is placed in modifier solution 30 minutes, is taken out, is placed in baking oven in 100 DEG C dry 3 Hour, it is cooled to room temperature, obtains modified polypropene bracket.
By 20g ferrous nitrate, 20g manganese nitrate, 20g sodium citrate is dissolved in 500mL deionized water, then is diluted to volume and is The activator solution of 1L.
Modified polypropene branch is placed in activator solution 30 minutes, takes out, is washed with deionized water, is dried, then set It 10 minutes in the sodium borohydride aqueous solution that weight percent concentration is 3%, takes out, cleans, polypropylene bracket must be activated.
By 20g neodymium nitrate, 20g cobalt nitrate, 40g zinc nitrate, 30g sodium dihydrogen phosphate, 60g sodium citrate, 3g dimethylamino Borine, 6g ammonium sulfate are dissolved in 500mL deionized water, then are diluted to the neodymium zinc cobalt electroless plating solution that volume is 1L.
Will activation polypropylene branch be placed in neodymium zinc cobalt electroless plating solution, in 75 DEG C chemical plating 3 hours, take out clean, dry It is dry, obtain neodymium zinc-cobalt alloy/polypropylene timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose are dissolved in 500mL deionized water, then are diluted to the simulated body fluid that volume is 1L.
Neodymium zinc-cobalt alloy/polypropylene timbering material is placed in simulated body fluid, is placed 180 days in 37 DEG C, is taken out, is surveyed Organic carbon spill-out in solution is tried, and compared with polypropylene timbering material, calculating organic carbon to overflow reduced rate is 99.6%；With The constituent content of Energy Dispersive X-ray detector (EDX) test bracket material, calculate neodymium, zinc, cobalt ions flood rate be respectively 0.32ppm,0.61ppm,0.77ppm；Bending modulus with universal testing machine test bracket material is 1.41GPa, with not The surface hardness of family name's hardometer test bracket material is 6.3.

Claims (1)

1. a kind of preparation method of neodymium zinc-cobalt alloy/polypropylene timbering material, it is characterised in that:
1) by polypropylene bracket successively with weight percent concentration be 10% hydrazine hydrate aqueous solution, 5% hydrogen peroxide solution, go Ionized water is cleaned, is dried；
2) clean polypropylene branch is placed in modifier solution 30 minutes, is taken out, is placed in baking oven small in 100 DEG C of dryings 3 When, it is cooled to room temperature, obtains modified polypropene bracket；
3) modified polypropene branch is placed in activator solution 30 minutes, takes out, is washed with deionized water, dried, then be placed in 10 minutes in the sodium borohydride aqueous solution that weight percent concentration is 3%, takes out, be washed with deionized water, obtain activation polypropylene Bracket；
4) will activation polypropylene branch be placed in neodymium zinc cobalt electroless plating solution, in 75 DEG C chemical plating 3 hours, take out clean, drying, Obtain neodymium zinc-cobalt alloy/polypropylene timbering material；
It is deionized water that wherein the formula of modifier solution, which is solvent, and various solute concentrations are respectively as follows: in solution
3~6g/L of 3-aminopropyltriethoxysilane concentration；
9~12g/L of cyanacrylate concentration；
1~3g/L of cyclohexanone peroxide concentration；
100~200g/L of acetone concentration；
It is deionized water that wherein the formula of activator solution, which is solvent, and various solute concentrations are respectively as follows: in solution
20~30g/L of ferrous nitrate concentration；
20~30g/L of manganese nitrate concentration；
20~30g/L of sodium citrate concentration；
It is deionized water that wherein the formula of neodymium zinc cobalt electroless plating solution, which is solvent, and various solute concentrations are respectively as follows: in solution
20~30g/L of neodymium nitrate concentration；
20~30g/L of nitric acid cobalt concentration；
40~60g/L of nitric acid zinc concentration；
30~60g/L of phosphate dihydrogen sodium concentration；
60~90g/L of sodium citrate concentration；
3~6g/L of dimethylamino borane concentration；
6~9g/L of ammonium sulfate concentrations；
Wherein neodymium zinc-cobalt alloy/polypropylene timbering material performance are as follows: Mohs' hardness can reach 6.3；Through 180 days simulation bodies Corrosion test, metal ion flood rate are less than 1ppm.
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