Superhydrophobic fluoride conversion coating on bioresorbable magnesium alloy——fabrication,characterization,degradation and cytocompatibility with BMSCs

A micro-nano structure CaF_(2)chemical conversion layer was prepared on fluoride-treated AZ31 alloy,then the composite fluoride conversion film(CaF_(2)/MgF_(2))was modified by stearic acid(SA)and fabricated a superhydrophobic surface.The fluoride-treated magnesium,fluoride conversion film and superhydrophobic coating were characterized by SEM,EDS,XRD and FTIR.The properties of coatings1 adhesion and corrosion resistance were evaluated via tape test and electrochemical measurement.The cytocompatibility of the MgF_(2),CaF_(2)and superhydrophobic CaF_(2)/SA surface was investigated with bone marrow-derived mesenchymal stem cells(BMSCs)by direct culture for 24 h.The results showed that the superhydrophobic fluoride conversion coating composed of inner MgF_(2)layer and the outer CaF_(2)/SA composite layer had an average water contact angle of 152°.SA infiltrated into the micro-nano structure CaF_(2)layer and formed a strong adhesion with CaF_(2)layer.Furthermore,the super-hydrophobic coating showed higher barrier properties and corrosion resistance compared with the fluoride conversion film and fluoride-treated AZ31 alloy.The BMSC adhesion test results demonstrated MgF_(2)CaF_(2)and CaF_(2)/SA coatings were all nontoxic to BMSC.At the condition of in direct contact with cells,MgF_(2)showed higher cell density and enhanced the BMSCs proliferation,while CaF_(2)and CaF_(2)/SA coating showed no statistically difference in cell density compared with glass reference but the CaF_(2)and CaF_(2)/SA coating were not conducive to BMSCs adhesion.

Influence of pH on the Formation, Composition and Protectiveness of Fluoride Conversion Film Deposited on AZ31 Magnesium Alloy in KF Solution

In deaerated 0.1 M KF solution at pH 5, pH 7.5 and pH 9, fluoride films were deposited on AZ31 magnesium (Mg) alloy at − 1.4 V vs saturated calomel electrode (SCE). The morphology, phase composition, elemental and compositional depth distribution of different fluoride films and their influences on the corrosion resistance of AZ31 Mg alloy were explored in detail. The results indicated that the films deposited at weak acidic and nearly neutral pH consisted of two layers with amorphous Mg(OH)_(2) and MgF_(2) as the inner layer, and Mg(OH)_(2), MgF_(2) and KMgF_(3) crystals the outer layer. The film deposited at alkaline pH was a monolayer structure consisting of amorphous Mg(OH)_(2) as the major constitute and MgF_(2) as the minor constitute. The protectiveness of fluoride film was intimately related to its composition and structure. The content and crystal regularity of KMgF_(3) were the two main factors influencing the protectiveness of fluoride film. The fluoride film deposited at pH 7.5 offered the best protection to AZ31 Mg alloy.

Effect of applied potential on the microstructure, composition and corrosion resistance evolution of fluoride conversion film on AZ31 magnesium alloy

AZ31 magnesium（Mg） alloy was potentiostatic polarized in 0.1 M deaerated KF solution with pH 7.5 from-0.4 V to-1.4 V with an interval of-0.2 V. The polarization process was described by the potentiostatic current decay. The resultant film was analyzed by scanning electron microscopy（SEM）, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS） and electrochemical impedance spectroscopy（EIS）. The results demonstrated that the deposited film included a Mg（OH）2/MgF2 containing inner layer and a Mg（OH）-2/MgF2/KMgF3 comprising outer layer. The high polarized potential produced high content of MgF2 but low content of KMgF3 and thin film. Conversely, the low polarized potential produced small content of MgF2 but high content of KMgF3 and thick film. The optimal corrosion resistance of the deposited film was obtained at-1.4 V, which was closely related with the content of MgF2 and KMgF3 and the film thickness.

Poly(vinylidene fluoride) membrane based thin film microextraction for enrichment of benzoylurea insecticides from water samples followed by their determination with HPLC

Thin-film microextraction（TFME）,a new geometry for solid-phase microextraction,has become an attractive sample-preparation technique.Compared to other microextraction approaches,the sensitivity of this technique was enhanced without sacrificing the sampling time due to the high surface area-tovolume ratio together with the increase of extraction-phase volume.In this paper,a new TFME method based on poly（vinylidene fluoride） membrane was developed for the extraction of benzoylurea insecticides（diflubenzuron,triflumuron,hexaflumuron and teflubenzuron） from water samples followed by their determination with high performance liquid chromatography-diode array detection.Under the optimal conditions,good linearity was observed over the concentration range of 0.5-100.0 ng/mL with correlation coefficient greater than 0.9994.The limits of detection（S/N = 3） of the method for the target analytes were 0.1 ng/mL.Mean recoveries ranged from 87.7% to 103.9% with relative standard deviations lower than 6.5%.The results indicated that the developed TFME method is simple,efficient,and cost effective.