CN107823707A - A kind of preparation method of honeycomb-patterned ordered porous graphite ene coatings - Google Patents

A kind of preparation method of honeycomb-patterned ordered porous graphite ene coatings Download PDF

Info

Publication number
CN107823707A
CN107823707A CN201711039964.7A CN201711039964A CN107823707A CN 107823707 A CN107823707 A CN 107823707A CN 201711039964 A CN201711039964 A CN 201711039964A CN 107823707 A CN107823707 A CN 107823707A
Authority
CN
China
Prior art keywords
preparation
porous
honeycomb
graphite ene
ene coatings
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711039964.7A
Other languages
Chinese (zh)
Other versions
CN107823707B (en
Inventor
赵长虹
朱新术
宋雪斌
张其清
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinxiang Medical University
Original Assignee
Xinxiang Medical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinxiang Medical University filed Critical Xinxiang Medical University
Priority to CN201711039964.7A priority Critical patent/CN107823707B/en
Publication of CN107823707A publication Critical patent/CN107823707A/en
Application granted granted Critical
Publication of CN107823707B publication Critical patent/CN107823707B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • 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

Abstract

The invention discloses a kind of preparation method of honeycomb-patterned ordered porous graphite ene coatings, using improved Hummers methods, using expanded graphite as raw material, prepares GO.BreathFigure self assemblies ordered porous structural requires that material is dissolved in organic solvent, GO hydrophilies are strong but dispersed low in organic solvent, GO can be transferred to the organic solvent phase such as chloroform from aqueous phase using the electrostatic interaction of cationic surfactant such as dioctadecylamine and GO, after to pretreatments such as Ti substrates cleanings, cellular porous GO layers are then prepared in Ti substrates using BreathFigure self-assembly methods.Porous GO layers reduce to obtain porous graphene layer through the reducing agent such as hydrazine hydrate or ascorbic acid.For the present invention using honeycomb-patterned ordered porous graphite ene coatings are prepared on titanium surface, the coating of preparation can not only provide antibiotic property, moreover it is possible to regulate and control the function of Gegenbaur's cell, promote the quick Integrated implant of bone titanium.

Description

A kind of preparation method of honeycomb-patterned ordered porous graphite ene coatings
Technical field
The invention belongs to medicine technology field, specifically, is related to a kind of system of honeycomb-patterned ordered porous graphite ene coatings Preparation Method.
Background technology
Bio-medical material can be diagnosed to body tissue, treated, replaced injury tissue, organ or promote its function, Belong to medicine equipment category, its research is the intercrossing frontier branch of science between biology, medical science, materialogy and chemistry, is studied The content almost whole field of covering material science and life science, there is the characteristics of knowledge, technology-intensive and multi-crossed disciplines.
Titanium alloy the research and development history of biomedical aspect can trace back to phase early 1940s, Bothe et al. first Pure titanium is incorporated into biomedical sector, and they are had found between titanium and mouse femur without any adverse reaction.Leventhal after 10 years Further research confirms the good biocompatibility of pure titanium.But because medical stainless steel, cochrome are in the secondary world Had started to during Great War it is prevailing, titanium alloy biomedical sector application and development it is slower.Since the sixties After pure titanium is used for mouth cavity planting body by Branemark, pure titanium has just obtained broad development, subsequent α as surgical implants material Type Titanium Alloy Ti3Al25V is also clinically used as femur and shin bone alternate material.
Medical titanium alloy implantation material surface lacks antibiotic property, the infection problems as caused by bacterial adhesion easily occurs.Titanium The anti-infective aspect of alloy implantation material surface, is modified using antimicrobial coating more, and still, the antiseptic such as addition antibiotic can be made Into bacterial resistance.Graphene is found to have produces antibacterial action by mechanical damage and oxidative stress etc., and this effect avoids Bacterial resistance problem.Loose structure has preferable porosity, can well stick with target cell, have and promote Gegenbaur's cell to increase Grow the effect of differentiation.
At present, in the prior art it is not yet found that preparing the ordered porous graphite ene coatings of nest shape in titanium implantation material surface Report.
The content of the invention
In order to overcome defect present in prior art, the present invention proposes a kind of honeycomb-patterned ordered porous graphite ene coatings Preparation method, using honeycomb-patterned ordered porous graphite ene coatings are prepared on titanium surface, the coating of preparation can not only provide Antibiotic property, moreover it is possible to regulate and control the function of Gegenbaur's cell, promote the quick Integrated implant of bone-titanium.
Its technical scheme is as follows：
A kind of preparation method of honeycomb-patterned ordered porous graphite ene coatings, comprises the following steps：
The preparation of step 1, GO：By 98% dense H of 46ml2SO4, 2g expanded graphites 500nm, 1g NaNO3Add 250mL circles In the flask of bottom, ice-water bath stirring；Then within an hour in six times by 6g KMnO4It is added in round-bottomed flask, then proceedes to Stirring 2 hours；Ice-water bath is replaced with oil bath, temperature is promoted to 35 DEG C to 40 DEG C, keeps reaction 1.5 hours；This stage oxidation Process slowly starts, and system viscosity constantly rises；Then, 100mL deionized waters are added into system, control system temperature is rapid Improve to 98 DEG C, and continue stirring 2.5 hours in this temperature；Finally, H is slowly added dropwise into system2O2Solution, until without gas Bubble produces；
Step 2, it is polished after titanium sheet be cleaned by ultrasonic 10 respectively in deionized water, ethanol, acetone, deionized water respectively Minute, nitrogen drying；
Step 3, Ti porous surface GO coatings are prepared using phase transfer combination Breath-Figure self-assembly methods.
Further, the detailed process of step 3 is：First by GO ultrasonic disperses in deionized water, stable disperse is formed Liquid, high speed centrifugation take the liquid that upper strata is mainly individual layer GO, adjust pH to 9.0 with 1M NaOH, then add cation form containing DODA The chloroformic solution of face activating agent, the negative electrical charge on GO surfaces form GO.DODA with the positive charge of DODA bands by electrostatic interaction Complex, GO can be transferred in chloroform phase from aqueous phase；GO chloroformic solution is dripped into Ti surfaces, while is passed through the gas of humidity Stream, chloroform volatilizees rapidly, causes Water vapor condensation to form water droplet template, the ordered porous GO structures of self assembly, treat water on GO surfaces After drop evaporation, loose structure remains；Obtained porous GO layers reduce to obtain porous graphite ene coatings using ascorbic acid.
Beneficial effects of the present invention are：
Using honeycomb-patterned ordered porous graphite ene coatings are prepared on titanium surface, the coating of preparation can not only carry the present invention For antibiotic property, moreover it is possible to regulate and control the function of Gegenbaur's cell, promote the quick Integrated implant of bone-titanium.
Brief description of the drawings
Fig. 1 Hummers methods prepare graphene oxide reagent addition flow chart；
Fig. 2 Ti porous surface GO coatings use phase transfer combination Breath-Figure self-assembly method preparation flow figures.
Embodiment
Technical scheme is described in more detail with reference to the accompanying drawings and detailed description.
1 GO preparation and sign
GO is prepared using improved Hummers methods, reagent adds flow as shown in figure 1, detailed process is as follows：
By 98% dense H of 46ml2SO4, 2g expanded graphites (500nm), 1gNaNO3Add in 250mL round-bottomed flasks, ice-water bath Stirring.Then within an hour in six times by 6g KMnO4It is added in round-bottomed flask, then proceedes to stirring 2 hours.Use oil bath Instead of ice-water bath, temperature is promoted to 35 DEG C to 40 DEG C, keeps reaction 1.5 hours.This stage oxidation process slowly starts, system Viscosity constantly rises.Then, 100mL deionized waters are added into system, control system temperature is improved to 98 DEG C rapidly, and in This temperature continues stirring 2.5 hours.Finally, H is slowly added dropwise into system2O2Solution, until bubble-free produces.
Prepared GO is washed using centrifugal process, and obtained reaction solution is dispensed to different centrifuge tubes, is added A certain amount of deionized water centrifuges 2min under 6000rpm, and removes supernatant liquor, and the step repeats repeatedly, until upper Layer liquid presents vaporific.Now, pH value test is carried out, if pH between 6-7, can be collected.For sediment, continue to add Enter a certain amount of deionized water and be ultrasonically treated 30min, then centrifuged using same method, and collect, to maximize yield.
After obtained GO is dried, a certain amount of powder is taken, its oxygen content and degree of oxidation are determined using elemental analyser；GO surpasses Sound is dispersed in water, and is spun to mica sheet, and its size and thickness are observed using AFM；The SP of carbon atom in GO2Hydridization and SP3Hydridization Characterized using Raman spectrum analyses.
The self assembly of the ordered porous graphite ene coatings in 2 Ti surfaces
Titanium sheet after polished is cleaned by ultrasonic 10 minutes respectively in deionized water, ethanol, acetone, deionized water respectively, Nitrogen dries up.
Ti porous surface GO coatings are prepared using phase transfer combination Breath-Figure self-assembly methods, its process such as Fig. 2 institutes Show, first by GO ultrasonic disperses in deionized water, form stable dispersion liquid, it is mainly individual layer GO that high speed centrifugation, which takes upper strata, Liquid, pH to 9.0 is adjusted with 1M NaOH, then adds the chloroformic solution of the cationic surfactant containing DODA, the negative electricity on GO surfaces Lotus and the positive charge of DODA bands form GO.DODA complexs by electrostatic interaction, GO can be transferred into chloroform from aqueous phase Xiang Zhong.GO chloroformic solution is dripped into Ti surfaces, while is passed through the air-flow of humidity, chloroform volatilizees rapidly, causes Water vapor condensation On GO surfaces, water droplet template is formed, the ordered porous GO structures of self assembly, after water droplet evaporation, loose structure remains.Obtain Porous GO layers reduce to obtain porous graphite ene coatings using ascorbic acid.
The foregoing is only a preferred embodiment of the present invention, protection scope of the present invention not limited to this, any ripe Those skilled in the art are known in the technical scope of present disclosure, the letter for the technical scheme that can be become apparent to Altered or equivalence replacement are each fallen within protection scope of the present invention.

Claims (2)

1. a kind of preparation method of honeycomb-patterned ordered porous graphite ene coatings, it is characterised in that comprise the following steps：
The preparation of step 1, GO：By 98% dense H of 46ml2SO4, 2g expanded graphites 500nm, 1g NaNO3250mL round bottoms are added to burn In bottle, ice-water bath stirring；Then within an hour in six times by 6g KMnO4It is added in round-bottomed flask, then proceedes to stirring 2 Hour；Ice-water bath is replaced with oil bath, temperature is promoted to 35 DEG C to 40 DEG C, keeps reaction 1.5 hours；This stage oxidation process is delayed Slow to start, system viscosity constantly rises；Then, 100mL deionized waters are added into system, control system temperature improves rapidly extremely 98 DEG C, and continue stirring 2.5 hours in this temperature；Finally, H is slowly added dropwise into system2O2Solution, until bubble-free produces；
Step 2, it is polished after titanium sheet be cleaned by ultrasonic 10 points respectively in deionized water, ethanol, acetone, deionized water respectively Clock, nitrogen drying；
Step 3, Ti porous surface GO coatings are prepared using phase transfer combination Breath-Figure self-assembly methods.
2. the preparation method of honeycomb-patterned ordered porous graphite ene coatings according to claim 1, it is characterised in that step 3 Detailed process be：First by GO ultrasonic disperses in deionized water, stable dispersion liquid is formed, high speed centrifugation takes upper strata main For individual layer GO liquid, pH to 9.0 is adjusted with 1M NaOH, then adds the chloroformic solution of the cationic surfactant containing DODA, GO The negative electrical charge on surface forms GO.DODA complexs with the positive charge of DODA bands by electrostatic interaction, and GO is shifted from aqueous phase Into chloroform phase；GO chloroformic solution is dripped into Ti surfaces, while is passed through the air-flow of humidity, chloroform volatilizees rapidly, causes water to steam Gas condenses in GO surfaces, forms water droplet template, the ordered porous GO structures of self assembly, after water droplet evaporation, loose structure retains Come；Obtained porous GO layers reduce to obtain porous graphite ene coatings using ascorbic acid.
CN201711039964.7A 2017-10-25 2017-10-25 Preparation method of honeycomb-shaped ordered porous graphene coating Active CN107823707B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711039964.7A CN107823707B (en) 2017-10-25 2017-10-25 Preparation method of honeycomb-shaped ordered porous graphene coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711039964.7A CN107823707B (en) 2017-10-25 2017-10-25 Preparation method of honeycomb-shaped ordered porous graphene coating

Publications (2)

Publication Number Publication Date
CN107823707A true CN107823707A (en) 2018-03-23
CN107823707B CN107823707B (en) 2021-06-25

Family

ID=61651128

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711039964.7A Active CN107823707B (en) 2017-10-25 2017-10-25 Preparation method of honeycomb-shaped ordered porous graphene coating

Country Status (1)

Country Link
CN (1) CN107823707B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104119529A (en) * 2014-08-02 2014-10-29 桂林理工大学 Preparation method of polyaniline/graphene composite material with nano tubular structure
CN105482139A (en) * 2016-01-18 2016-04-13 浙江工业大学 Preparation method of porous polystyrene thin-film material with uniform pore diameters
CN106245091A (en) * 2016-07-26 2016-12-21 斌源材料科技（上海）有限公司 Composite titania material and its preparation method and application
US20170088969A1 (en) * 2015-09-25 2017-03-30 Jackson State University Method for obtaining a composite coating on titanium implants for tissue engineering

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104119529A (en) * 2014-08-02 2014-10-29 桂林理工大学 Preparation method of polyaniline/graphene composite material with nano tubular structure
US20170088969A1 (en) * 2015-09-25 2017-03-30 Jackson State University Method for obtaining a composite coating on titanium implants for tissue engineering
CN105482139A (en) * 2016-01-18 2016-04-13 浙江工业大学 Preparation method of porous polystyrene thin-film material with uniform pore diameters
CN106245091A (en) * 2016-07-26 2016-12-21 斌源材料科技（上海）有限公司 Composite titania material and its preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HONGMIN MA等: "Assembly of graphene nanocomposites into honeycomb-structured macroporous films with enhanced hydrophobicity", 《NEW JOURNAL OF CHEMISTRY》 *
TANG, H等: "Self-assembly of Si/honeycomb reduced graphene oxide composite film as a binder-free and flexible anode for Li-ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
赵长虹: "基于聚乳酸和氧化石墨烯的功能化改性及生物医学应用研究", 《中国博士学位论文全文数据库医药卫生科技辑》 *

Also Published As

Publication number Publication date
CN107823707B (en) 2021-06-25

Similar Documents

Publication Publication Date Title
EP2736544B1 (en) Tissue scaffold
CN109069690A (en) Planting body and its manufacturing method with nano-pattern dimple surface
CN106606801B (en) A kind of Zn-ZnO system kirsite and the preparation method and application thereof
CN105126167A (en) 3D (three-dimensional) printing type porous metal scaffold with superficial nanocomposite coatings and preparation of 3D printing type porous metal scaffold
CN104815351B (en) Myocardial bionic scaffold made from composite conducting material and preparation method thereof
CN102793947B (en) Degradable magnesium and surface modification method of alloy thereof
CN107190191B (en) A kind of biological medical magnesium alloy and preparation method thereof
CN105060280A (en) Preparation method of graphene film of titanium or titanium alloy surface
CN113529158B (en) Process for preparing porous structure on surface of TC4 titanium alloy by electrochemical dealloying method
Feng et al. Self-adhesion conductive sub-micron fiber cardiac patch from shape memory polymers to promote electrical signal transduction function
CN106011815A (en) Preparation method for hybrid composite coating used for magnesium-based biological material surface medication
CN112618788A (en) Bone defect repair material based on modified perovskite quantum dots/amino carbon quantum dots and preparation method thereof
CN108478298A (en) A kind of planting body of polysaccharide coatings and preparation method thereof containing in combination with growth factor
CN106606800B (en) A kind of Zn-Fe system kirsite and the preparation method and application thereof
Liu et al. Tea polyphenol-reduced graphene oxide deposition on titanium surface enhances osteoblast bioactivity
CN103520776B (en) Medical titanium substrate material and manufacturing method thereof
Ye et al. Research on micro-structure and hemo-compatibility of the artificial heart valve surface
CN113174592B (en) Preparation and application of coating for improving biocompatibility of medical zinc/zinc alloy surface
CN108004527A (en) A kind of preparation method of zinc doping hydroxyapatite coating layer for magnesium alloy materials
CN106606806B (en) A kind of Zn-Mg1Ca system kirsite and the preparation method and application thereof
CN107823707A (en) A kind of preparation method of honeycomb-patterned ordered porous graphite ene coatings
CN107805625A (en) A kind of graphene culture medium bottom and preparation method thereof and the application in terms of multipotential stem cell cultivation, differentiation and transplanting
CN108815571A (en) A kind of preparation method of modified by silver crystal form titanium dioxide nanotube layer
CN106609327B (en) A kind of Zn-HAP systems kirsite and preparation method and application
CN107596453A (en) A kind of 3D printing composite magnetic metallic support and its application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant