Characterization of coated particulate fillers

Stearic acid coated samples of porous and non-porous grades of magnesium hydroxide and calcium carbonate have been characterized using diffuse reflectance infra red (DRIFT), and X-ray photoelectron spectroscopy (XPS). Using DRIFT, the signal due to the reacted coating reached a plateau at a coating level dependent on the filler surface area. XPS showed that coating thickness increased with the amount of coating, slope changes being observed in plots at lower levels of applied coating than those observed by DRIFT. The differences between the measurements for the two techniques is attributed to their different sampling depths. The FTIR having a greater sampling depth probes the internal surface area of the agglomerates present in the porous material, whereas XPS does not. The surface chemistry of the two types of coated filler is compared.     

新型保温隔热外墙涂料的研制

以碳酸钙、金红石型二氧化钛、空心玻璃微珠、氧化锌为颜填料,以苯丙乳液为主成膜物,制备出的建筑外墙保温隔热涂料,其常规性能符合外墙涂料的相关标准要求。研究了添加碳酸钙、金红石型二氧化钛和氧化锌三种填料及复合添加四种填料对涂层隔热性能的影响。结果表明：添加碳酸钙、金红石型二氧化钛和氧化锌可提高涂层隔热性能;复合掺入碳酸钙、金红石型二氧化钛、氧化锌和空心玻璃微珠可进一步提高涂层隔热性能。掺加15％碳酸钙、7％金红石型二氧化钛、5％氧化锌和8％空心玻璃微珠时,隔热温差为7．9℃,导热系数为0．0767W／（m·K）,具有明显的保温隔热效果。     

Rheological characterization of polypropylene filled with magnesium hydroxide

Consideration is given to the dynamic viscoelastic and shear flow properties of magnesium hydroxide-filled polypropylene, at a filler concentration of 60 wt%. Five variants of magnesium hydroxide were used, one surface-treated with magnesium stearate. The results reported illustrate the effects of filler particle size, morphology and surface coating on the rheology of the composites. The presence of magnesium hydroxide caused a significant increase in the shear viscosity of polypropylene relative to unfilled polymer, although this was much less pronounced using surface-treated filler, particularly at low shear rates. Complex viscosity and storage modulus data, obtained at very low shear rates (0.002 s^–1), demonstrated the presence of a critical shear yield stress for flow to occur, which was greatest for compositions containing uncoated fillers with small particle size. These observations are discussed in terms of structure formation between the particles. Results obtained from capillary and dynamic measurements of melt flow were found to follow the Cox-Merz rule.     

直接沉淀法制备疏水性氢氧化镁及其表征

以苦卤和氨水为原料,硬脂酸镧为改性剂,采用常温一步直接沉淀法制备疏水性氢氧化镁纳米粒子;用扫描电子显微镜、傅里叶红外光谱、热重分析、X射线衍射、疏水性分析等手段对所得产物进行表征分析并进行疏水性测试。结果表明,在合成的过程中,硬脂酸镧通过化学反应改变了氢氧化镁的表面性质,改性后的Mg(OH)2为非极性,可漂浮在水面,表现为疏水性;硬脂酸镧并未改变Mg(OH)2的晶型,但是在X射线衍射中出现La(OH)3的杂质峰;硬脂酸根离子吸附在Mg(OH)2纳米粒子表面,使其表面有机化,同时提高了分散性和热稳定性。     

Ultra-fine dispersible powders coated with l-Leucine via two-step co-milling

Dispersion of ultrafine powders is difficult due to their high cohesion and consequent agglomeration. Dry coating with additives such as nano-silica, magnesium stearate (MgSt), or Leucine (Leu), an amino acid, may help mitigate this problem. Unfortunately, when the powders to be coated are very fine, the additives such as MgSt or Leu need to be of even finer size, requiring a separate milling process. Here, a two-step co-milling process is investigated to produce well dispersible inhalable size range (<5 µm) particles. The main advantage is that the powder to be coated and additives have starting size of several hundred microns and do not require separate pre-milling. In the first step, Potassium Chloride (KCl), used as a surrogate API, and Leu are pre-milled in a ball mill to achieve KCl coated with Leu of ～10?µm. In the second step, simultaneous co-milling via jet-milling of pre-coated KCl down to inhalable size KCl, coated with Leu is done. The dispersibility of coated KCl was assessed through laser diffraction of dry powder at low dispersion pressure (Sympatec Rodos-Helos), corroborated via scanning electron microscopy (SEM), and FT4 powder tester measuring flow function coefficient (FFC), conditioned bulk density, and aerated energy. This assessment revealed that about 2?wt% Leu was adequate to provide best overall dispersibility. The dispersibility of milled KCl after coating with Leu was found to be better compared with uncoated and MgSt or nano-silica coated KCl. Overall, this two-step co-milling of KCl with 2?wt% Leu yielded well-dispersible, <5?µm particles from starting particles of two orders of magnitude larger sizes.     

Morphology of calcium carbonate coating on amorphous silicate powder

The amorphous silicate powders containing sodium, calcium,barium and magnesium were prepared by sol-gel and ion-exchangemethod, and calcium carbonate was coated on the powders for thepurpose of industrial re-circulation of calcium carbonate. Thecalcium carbonate powder with micro pores was obtained bycoating on amorphous CaO-SiO₂ powder, and the pore sizedistribution would be influenced by calcium on the surface ofthe powder. The coating on amorphous MgO-SiO₂ powderresulted in a hedgehog-like powder, which allowed needle-likecrystal extended radially, and the coated powder was the mixedphase of aragonite and calcite. The use of amorphousBaO-SiO₂ and Na₂O-SiO₂ powders also led to the coatingpowder with the single phase of calcite. The morphology ofcalcium carbonate coating would be ascribed to cations on thesurface of the amorphous silicate powders, because the amount ofcations that would be dissolved in soaking solution was smalland insufficient to affect the morphology.     

Zinc hydroxystannate-coated metal hydroxide fire retardants: Fire performance and substrate-coating interactions

Fire retardant (FR) properties, including limiting oxygen index, peak rate of heat release and smoke parameter have been measured and compared for unfilled and filled polyvinyl-chloride (PVC) based cable formulations, containing various amounts of uncoated and zinc-hydroxystannate (ZHS)-coated alumina trihydrate (ATH) and magnesium hydroxide (MH) fillers. Uncoated ATH or MH proved to be efficient FR additives, but when coated with ZHS, further improvements were observed. ATH was more effective than MH in both uncoated and ZHS-coated forms. For a halogen-free ethylene-vinyl acetate (EVA) cable formulation, the content of vinyl acetate and loading of ZHS-coated ATH required to yield optimum FR properties was determined. The interaction between ATH substrate and ZHS coating was also studied by X-ray photoelectron spectroscopy and diffuse reflectance infrared Fourier-transform spectroscopy, using samples with ZHS-contents ranging from 1 to 15 wt%. An increase in the binding energies of the Zn 2p_3/2 and Sn 3d_5/2 peaks was found, together with alterations in the positions of the (Sn)O—H stretching bands. There was no evidence for condensation and the formation of Al—O—Sn bonds.     

Polylactic acid coating on a biodegradable magnesium alloy: An in vitro degradation study by electrochemical impedance spectroscopy

Polylactic acid (PLA) was coated on a biodegradable magnesium alloy, AZ91, using spin coating technique for temporary implant applications. The degradation behaviour of the coated alloy samples was evaluated using electrochemical impedance spectroscopy (EIS) method in simulated body fluid (SBF). EIS results suggested that the PLA coating enhanced the degradation resistance of the alloy significantly. Increase in the PLA coating thickness was found to increase the degradation resistance, but resulted in poor adhesion. Long-term EIS experiments of the PLA coated samples suggested that their degradation resistance gradually decreased with increase in SBF exposure time. However, the degradation resistance of the PLA coated samples was significantly higher than that of the bare metal even after a 48 h exposure to SBF.     

Hybrid coating on a magnesium alloy for minimizing the localized degradation for load-bearing biodegradable mini-implant applications

The effect of a hybrid coating, calcium phosphate (CaP) + polylactic acid (PLA), on a magnesium alloy on its in vitro degradation (general and localized) behaviour was studied for potential load-bearing biodegradable mini-implant applications. CaP was coated on a magnesium alloy, AZ91, using an electrochemical deposition method. A spin coating method was used to coat PLA on the CaP coated alloy. In vitro degradation performance of the alloy with hybrid coating was evaluated using electrochemical impedance spectroscopy (EIS) in simulated body fluid (SBF). The EIS results showed that the hybrid coating enhanced the degradation resistance of the alloy by more than two-order of magnitude as compared to the bare alloy and one-order of magnitude higher than that of the CaP coated alloy, after 1 h exposure in simulated body fluid (SBF). Long-term (48 h) EIS results also confirmed that the hybrid coating performed better than the bare alloy and the CaP coated alloy. Importantly, the hybrid coating improved the localized degradation resistance of the alloy significantly, which is critical for better in service mechanical integrity.     

Potentiostatic pulse-deposition of calcium phosphate on magnesium alloy for temporary implant applications — An in vitro corrosion study

In this study, a magnesium alloy (AZ91) was coated with calcium phosphate using potentiostatic pulse-potential and constant-potential methods and the in vitro corrosion behaviour of the coated samples was compared with the bare metal. In vitro corrosion studies were carried out using electrochemical impedance spectroscopy and potentiodynamic polarization in simulated body fluid (SBF) at 37 °C. Calcium phosphate coatings enhanced the corrosion resistance of the alloy, however, the pulse-potential coating performed better than the constant-potential coating. The pulse-potential coating exhibited ~ 3 times higher polarization resistance than that of the constant-potential coating. The corrosion current density obtained from the potentiodynamic polarization curves was significantly less (~ 60%) for the pulse-deposition coating as compared to the constant-potential coating. Post-corrosion analysis revealed only slight corrosion on the pulse-potential coating, whereas the constant-potential coating exhibited a large number of corrosion particles attached to the coating. The better in vitro corrosion performance of the pulse-potential coating can be attributed to the closely packed calcium phosphate particles.     

Fabrication of Superhydrophobic Zinc Stearate Hierarchical Surfaces from Different Precursors

The fabrication of zinc stearate superhydrophobic hierarchical surfaces from two precursors by a simple wet chemical route and its wettability is reported. The zinc stearate coatings were prepared from a single pot using ethanolic solutions of zinc acetate/zinc nitrate and stearic acid. The coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, water contact angle, and sliding angle measurements. The coatings obtained from zinc acetate precursor showed superhydrophobicity (WCA >150°) even at lower precursor concentrations. The morphology of the coatings varied with the nature as well as the concentration of the precursors.     

二水磷酸氢钙包覆镁粉的组织及其在NaCl溶液中的腐蚀行为

运用液相化学沉积技术制备了二水磷酸氢钙包覆镁粉粉末。利用扫描电镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)及傅里叶变换红外光谱仪(FT-IR)分析包覆层特征,用比表面积和孔隙度分析仪测定包覆前后粉末的比表面积,并通过浸泡实验研究包覆粉末的腐蚀行为。结果表明,包覆处理后的镁粉颗粒仍保持球形,表面形成了一层厚度2~4μm细片状的二水磷酸氢钙(DCPD),与未包覆粉末相比,其比表面积增加约60倍,在3.5%(质量分数)NaCl溶液中的耐腐蚀性能提高四个数量级。     

无机晶须在聚合物中的应用

本文针对无机晶须的各种优异性能 ,对钛酸钾晶须、硼酸铝晶须、氧化锌晶须、镁盐晶须、硫酸钙晶须、碳酸钙晶须等在聚合物中用于增强、增韧及提高耐磨性、耐热性 ,改善电性能、减振抗冲、隔音以及改善加工性能等方面的情况进行了详细的综述     

In vitro performance of magnesium processed by different routes for bone regeneration applications

Magnesium processed by powder metallurgy (PM) and casting was investigated for potential use in bone regeneration applications. To reduce its corrosion rate, magnesium was surface-modified by a chemical conversion treatment in hydrofluoric acid (HF). In vitro behaviour was evaluated in terms of biodegradation and osteoblastic cell response. The metallurgical route used to produce magnesium has more significant consequences on biodegradation and biocompatibility than the effects of the surface coating. The coated magnesium processed by casting exhibits the best in vitro performance.     

Doped nanocrystalline calcium carbonate phosphates

The formation of nanocrystalline calcium carbonate phosphates doped with Fe²⁺, Mg², Zn²⁺, K⁺, Si⁴⁺, and Mn²⁺ has been studied by X-ray diffraction, IR spectroscopy, differential thermal analysis, and energy dispersive X-ray fluorescence analysis. The results indicate that the synthesis involves the formation of hydroxy carbonate complexes from the three calcium carbonate polymorphs (calcite, vaterite, and aragonite) in a solution of ammonium chloride and ammonium carbonate, followed by reaction with orthophosphoric acid. This ensures the preparation of a bioactive material based on chlorophosphates, octacalcium hydrogen phosphate, and calcium chloride hydroxide phosphates containing cation vacancies. Particle-size analysis data show that the materials contain nanoparticles down to 10 nm in size. Heat treatment of the doped calcium carbonate phosphates produces calcium hydroxyapatite containing cation vacancies, which can be used as a bioactive ceramic.     

Corrosion behavior of friction stir welded AZ31B magnesium alloy with plasma electrolytic oxidation coating formed in silicate electrolyte

A protective ceramic coating of about 50 μm thick on a friction stir welded (FSW) joint of AZ31B magnesium alloy was prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte. Electrochemical corrosion behavior of uncoated and coated FSW joints was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The equivalent circuits of EIS plots for uncoated and coated FSW magnesium alloy were suggested. The corrosion resistance of FSW magnesium alloy depended on microstructure of the FSW joint. The heat-affected zone with severe grain growth was more susceptible to corrosion than the stir zone and base metal. The PEO coating consisted of a porous outer layer and a dense inner layer. The inner layer of PEO coating played a key role on corrosion protection of the FSW joint of magnesium alloy. Meanwhile, corrosion potential, corrosion current density and impedance at different zones of coated FSW joint were almost the same. The PEO surface treatment significantly improved the corrosion resistance of FSW joints of AZ31B magnesium alloy.     

X-ray photoelectron spectroscopy investigations of zinc–magnesium alloy coated steel

The coating layer composition depth profiles and element chemical states of zinc–magnesium alloy coated steel were investigated by X-ray photoelectron spectroscopy depth profiling. Through the analysis of photoelectron signals and Auger signals of different elements on different depth planes of the coating layer, it can be found that the surface of the coating layer contains MgCO₃, MgO, Mg(OH)₂, metallic Mg, metallic Zn and some complex zinc compounds. Under the surface, there is a Zn₂Mg alloy layer with the thickness of about 300 nm accompanied with MgO and Mg(OH)₂ in the layer. There is a transitional layer with the thickness of about 200 nm between the Zn₂Mg alloy layer and the pure Zn layer, whose components consist of zinc–magnesium alloy without fixed stoichiometry, a little MgO and a little Mg(OH)₂.     

Thermal and morphological characterization of poly(ethylene terephthalate)/calcium carbonate nanocomposites

Nanocomposites composed of poly(ethylene terephthalate) (PET) filled with calcium carbonate particles of nanometer scale were prepared by polymerizing the polyester in the presence of the nanosized fillers. Besides plain calcium carbonate, carbonate nanoparticles coated with stearic acid were also used, in order to improve the compatibility between the polymeric matrix and nanofillers. Morphological analysis evidenced a good dispersion of both the nanopowders into the PET matrix, especially in the case of coated calcium carbonate. The strong interfacial adhesion between the two phases is also responsible for the increase of the glass transition and melting temperatures in the nanocomposites compared to plain PET. Finally, non-isothermal crystallization studies revealed that the coated CaCO₃ is a good nucleating agent for PET. Analysis of non-isothermal crystallization data with the Ozawa theory was successful for plain PET and PET/un-CaCO₃, but this method failed to describe the dynamic solidification of the PET/c-CaCO₃ nanocomposite.     

硅丙乳液包覆Mg(OH)2核壳结构纳米粒子的制备与表征

为有效提高Mg(OH)_2纳米粒子在硅丙乳液中的相容性与分散稳定性,在油酸修饰Mg(OH)_2纳米粒子的基础上,以甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸与乙烯基三乙氧基硅烷为共聚单体,通过乳液聚合法制备出具有核壳结构的硅丙乳液包覆Mg(OH)_2复合材料。利用傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、透射电子显微镜(TEM)等测试手段对样品结构、形貌进行了表征。通过燃烧实验,研究了硅丙乳液包覆Mg(OH)_2纳米粒子对水性防火涂料阻燃性能的影响。结果表明,油酸通过酯化作用修饰在Mg(OH)_2纳米粒子表面,借助油酸分子中双键结构,丙烯酸类混合单体在纳米Mg(OH)_2表面完成聚合过程,形成以Mg(OH)_2纳米粒子为核、硅丙乳液为壳的复合材料。XRD与热分析表明经硅丙乳液包覆的纳米Mg(OH)_2晶体结构与热稳定性能未受影响。此外,掺杂0.1%(质量分数)的硅丙乳液包覆Mg(OH)_2可使水性防火涂料阻燃时间延长至113 min,较未掺杂水性涂料阻燃时间(91min)提高约23%。     

Fluoride Conversion Coating on Biodegradable AZ31B Magnesium Alloy

A fluoride conversion coating was successfully prepared on AZ31B magnesium alloy by chemical reaction in hydrofluoric acid. Morphologies, composition, bonding strength, corrosion properties, in vitro cytotoxicity and antibacterial properties of the coating were investigated, respectively. The scanning electron microscopy observations revealed a dense coating with some irregular pores. The thin-film X-ray diffraction analysis indicated that the coating was mainly composed of MgO and MgF2. The electrochemical impedance spectroscopy results showed that the fluoride conversion coating significantly improved the corrosion resistance of AZ31B. The hydroxyapatite formed on the surface of the fluoride coated AZ31 B after being immersed in the simulated blood plasma indicated the good bioactivity of the material. The in vitro cytotoxicity test showed that the fluoride coated AZ31B alloy was not toxic to BMMSCs （human bone marrow-derived mesenchymal stem cells）. It was also found that the fluoride coated AZ31 B alloy had antibacterial capability.