Research Progress on the Preparation of Inorganic/Natural Materials Composite Microspheres

Microspheres are a new type of drug carrier with great potential for development and application.Natural polymers have good biocompatibility,biodegradability,and are easily dispersed in living organisms,making them suitable for preparing microspheres.Inorganic materials(mainly inorganic minerals)have excellent mechanical properties and are inexpensive and easy to obtain.Through the coupling and hybridization of natural polymers and inorganic materials,they can complement each other's advantages and synergistically enhance efficiency,resulting in many excellent physical and chemical properties.Inorganic materials/natural polymer composite microspheres can be prepared by modifying natural polymers with inorganic materials through various methods such as emulsification crosslinking,solution mixing,in-situ synthesis,extrusion,etc.The application of inorganic materials/natural polymer composite microspheres in drug delivery systems has significant sustained-release effects,is safe and non-toxic,and the cost of carrier materials is relatively low,which has certain significance for the development of new drug carriers.This article reviews the recent research on the preparation,drug loading and release properties of inorganic material/natural polymer composite microspheres,analyzes the advantages and disadvantages of commonly used preparation methods,and looks forward to the development direction of composite microspheres.

Template synthesis of copper azide primary explosive through Cu2O@HKUST-1 core-shell composite prepared by “bottle around ship” method

Copper azide(CA), as a primary explosive with high energy density, has not been practically used so far because of its high electrostatic sensitivity. The Cu2O@HKUST-1 core-shell structure hybrid material was synthesized by the “bottle around ship” methodology in this research by regulating the dissolution rate of Cu2O and the generation rate of metal-organic framework(MOF) materials. Cu2O@HKUST-1 was carbonized to form a Cu O@porous carbon(CuO@PC) composite material. CuO@PC was synthesized into a copper azide(CA) @PC composite energetic material through a gas-solid phase in-situ azidation reaction.CA is encapsulated in PC framework, which acts as a nanoscale Faraday cage, and its excellent electrical conductivity prevents electrostatic charges from accumulating on the energetic material’s surface. The CA@PC composite energetic material has a CA content of 89.6%, and its electrostatic safety is nearly 30times that of pure CA(1.47 mJ compared to 0.05 mJ). CA@PC delivers an outstanding balance of safety and energy density compared to similar materials.

Synthesis of Core-shell ZSM-5@ Ordered Mesoporous Silica by Tetradecylamine Surfactant

A core-shell composite consisting of ZSM-5 zeolite as the core and ordered mesoporous silica as the shell was prepared by a surfactant-controlled sol-gel process and using tetradecylamine(TDA) as the template and Tetraethylorthosilicate(TEOS) as the silica precursor.The pores of the silica shell were found to be ordered and perpendicular to the crystal faces of the zeolite core.The thickness of the shell in the coreshell structured composite can be adjusted in the range of 20-90 nm,while the surface morphology and the pore size distribution were modified by changing the mass ratio of TEOS to zeolite.The composite molecular sieves have higher surface area for capturing molecules than ZSM-5,and with the increase of mesoporous shell layer,the ZSM-5@SiO_(2)-x composites show stronger adsorption capacity of butyraldehyde.However,when the shell thickness exceeds 90 nm,the adsorption capacity of butyraldehyde decreases instead.The composites have a huge potential for environmental applications.

Preparation and characterization of composite microspheres of nano zinc ferrite/poly(D,L-lactide-co-alanine)

Magnetic nano zinc ferrite fliuds were synthesized using an improved liquid phase chemical method, which would be used to replace tradditional iron oxides magnetic material. A novel copolymer （PLAA） with D, L-lactide （D, L-LA） and alanine was synthesized using stannous octoate as initiator. Magnetic polymer microspheres were fabricated with nano zinc ferrite fluid coated with alanine modified poly lactide. These as-prepared zinc ferrite fluids, modified poly lactide and magnetic composites, were characterized with X-ray diffraction diffractometer, FT-IR spectrometer, nuclear magnetic resonance spectrometer, scanning electron microscope, transmission electron microscope, vibrating sample magnetometer, and thermogravimetric analyzer. The results demonstrate that the as-prepared zinc ferrite is spinel type of ZnFe2O4 nano crystals with particle size of 20-45 nm and magnetization of 32×10^-3 A.m2. Alanine is copolymerized with lactide, and the prepared composite magnetic microsphere is coated with the modified polylactide, with mass fraction of 45.5% of PLA, particle size ranging from 80-300 nm, and magnetization of 10.6×10^-3 A·m^2, which suggests ZnFe2O4 enjoys a stable magnetization after being coated by polymer.

Hollow Carbon Microspheres/MnO_2 Nanosheets Composites:Hydrothermal Synthesis and Electrochemical Behaviors

This article reported the electrochemical behaviors of a novel hollow carbon microspheres/manganese dioxide nanosheets(micro-HC/nano-MnO2) composite prepared by an in situ self-limiting deposition method under hydrothermal condition. The results of scanning electron microscopy reveal that MnO2 nanosheets homogeneously grow onto the surface of micro-HC to form a loose-packed microstructure. The quantity of MnO2 required in the electrode layer has thereby been reduced significantly, and higher specific capacitances have been achieved. The micro-HC/nano-MnO2 electrode presents a high capacitance of 239.0 F g-1 at a current density of 5 m A cm-2, which is a strong promise for high-rate electrochemical capacitive energy storage applications.

Facile preparation of core-shell Si@Li4Ti5O12 nanocomposite as large-capacity lithium-ion battery anode

As a promising alternative anode material,silicon(Si)presents a larger capacity than the commercial anode to achieve large capacity lithium-ion batteries.However,the application of pure Si as anode is hampered by limitations such as volume expansion,low conductivity and unstable solid electrolyte interphase.To break through these limitations,the core-shell Si@Li4Ti5O12nanocomposite,which was prepared via in-situ self-assembly reaction and decompressive boiling fast concentration method,was proposed in this work.This anode combines the advantages of nano-sized Si particle and pure Li4Ti5O12(LTO)coating layer,improving the performance of the lithium-ion batteries.The Si@Li4Ti5O12 anode displays a high initial discharge/charge specific capacity of 1756/1383 m Ahg^-1 at 500 mAg^-1(representing high initial coulombic efficiency of 78.8%),a large rate capability(specific capacity of 620 mAhg^-1 at4000 mAg^-1),an outstanding cycling stability(reversible specific capacity of 883 mAhg^-1 after 150 cycles)and a low volume expansion rate(only 3.3% after 150 cycles).Moreover,the synthesis process shows the merits of efficiency,simplicity,and economy,providing a reliable method to fabricate large capacity Si@Li4Ti5O12nanocomposite anode materials for practical lithium-ion batteries.

Research on properties of hollow glass microspheres/epoxy resin composites applied in deep rock in-situ temperature-preserved coring

Deep petroleum resources are in a high-temperature environment.However,the traditional deep rock coring method has no temperature preserved measures and ignores the effect of temperature on rock porosity and permeability,which will lead to the distortion of the petroleum resources reserves assessment.Therefore,the hollow glass microspheres/epoxy resin(HGM/EP)composites were innovatively proposed as temperature preserved materials for in-situ temperature-preserved coring(ITP-Coring),and the physical,mechanical,and temperature preserved properties were evaluated.The results indicated that:As the HGM content increased,the density and mechanical properties of the composites gradually decreased,while the water absorption was deficient without hydrostatic pressure.For composites with 50 vol%HGM,when the hydrostatic pressure reached 60 MPa,the water absorption was above 30.19%,and the physical and mechanical properties of composites were weakened.When the hydrostatic pressure was lower than 40 MPa,the mechanical properties and thermal conductivity of composites were almost unchanged.Therefore,the composites with 50 vol%HGM can be used for ITPCoring operations in deep environments with the highest hydrostatic pressure of 40 MPa.Finally,to further understand the temperature preserved performance of composites in practical applications,the temperature preserved properties were measured.An unsteady-state heat transfer model was established based on the test results,then the theoretical change of the core temperature during the coring process was obtained.The above tests results can provide a research basis for deep rock in-situ temperature preserved corer and support accurate assessment of deep petroleum reserves.

Synthesis of carbon-coated cobalt ferrite core-shell structure composite:A method for enhancing electromagnetic wave absorption properties by adjusting impedance matching

Cobalt ferrite has problems such as poor impedance matching and high density,which results in unsatisfactory electromagnetic wave(EMW)absorption performance.In this study,the CoFe_(2)O_(4)@C core-shell structure composite was synthesized by a two-step hydrothermal method.X-ray diffraction,transmission electron microscopy,Fourier transform infrared spectroscopy,thermogravimetric analysis,and vector network analysis et al.were used to test the structure and EMW absorption properties of CoFe_(2)O_(4)@C composite.The results show that the reflection loss(RL)of the CoFe_(2)O_(4)@C composite reaches the maximum value of25.66 dB at 13.92 GHz,and the effective absorbing band(EAB)is 4.59 GHz(11.20-15.79 GHz)when the carbon mass content is 6.01%.The RL and EAB of CoFe_(2)O_(4)@C composite are increased by 219.55%and 4.59 GHz respectively,and the density is decreased by 20.78%compared with the cobalt ferrite.Such enhanced EMW absorption properties of CoFe_(2)O_(4)@C composite are attributed to the attenuation caused by the strong natural resonance of the cobalt ferrite,moreover,the carbon coating layer adjusts the impedance matching of the composite,and the introduced dipole polarization and interface polarization can cause multiple Debye relaxation processes.

Determination of Triclocarban, Triclosan and Methyl-Triclosan in Environmental Water by Silicon Dioxide/Polystyrene Composite Microspheres Solid-Phase Extraction Combined with HPLC-ESI-MS

This paper developed a sensitive and efficient analytical method for triclocarban (TCC), triclosan (TCS) and Methyl-triclosan (MTCS) determination in environmental water, which involves enrichment by using silicon dioxide/polystyrene composite microspheres solid-phase extraction and detection with HPLC-ESI-MS. The influence of several operational parameters, including the eluant and its volume, the flow rate and acidity of water sample were investigated and optimized. Under the optimum conditions, the limits of detection were 1.0 ng/L, 2.5 and 4.5 ng/L for TCC, TCS, and MTCS, respectively. The linearity of the method was observed in the range of 5-2000 ng/L, with correlation coefficients (r2) >.99. The spiked recoveries of TCC, TCS and MTCS in water sampleswereachieved in the range of 89.5% -96.8% with RSD below 5.7%. The proposed method has been successfully applied to analyze real water samples and satisfactory results were achieved.

Preparation and Properties of Guiqi Polysaccharides/Chitosan/Alginate Composite Hydrogel Microspheres

A series of the Guiqi polysaccharides/chitosan/alginate composite hydrogel microspheres(GPcM)with different particle sizes were prepared with Guiqi polysaccharides(GP),chitosan(CS)and sodium alginate(Alg).The optimum preparation process was also determined by single factor and orthogonal experiment analysis.The GPcM were characterized by fourier transform infrared spectroscopy(FT-IR),scanning electron microscope(SEM),drug loading efficiency test(LE),encapsulation efficiency test(EE)and in vitro release study.The results showed that the Guiqi polysaccharides chitosan hydrogel(GPCH)and sodium alginate hydrogel(SAH)formed a crossover system in GPcM.The GPcM have a uniform particle size ranging from 395.1μm to 841.5μm.The drug loading efficiency and encapsulation efficiency of the GPcM were 56.3%and 72.6%,respectively.The bovine serum albumin(BSA)loaded in the GPcM released slowly within 180 h.The results suggested that the GPcM may have potential application value in drug sustained and controlled release system.

Application of Monodisperse Thermo-Responsive Composite Microgels with Core-Shell Structure Based on Au@Ag Bimetallic Nanorod as Core in Surface Enhanced Raman Spectroscopy Substrate

The monodisperse Au@Ag bimetallic nanorod is encapsulated by crosslinked poly( N-isopropylacrylamide)( PNIPAM) to produce thermo-responsive composite microgel with well-defined core-shell structure( Au@ Ag NR@ PNIPAM microgel)by seed-precipitation polymerization method using butenoic acid modified Au @ Ag NRs as seeds. When the temperature of the aqueous medium increases from 20℃ to 50℃,the localized surface plasmon resonance( LSPR) band of the entrapped Au @ Ag NR is pronouncedly red-shifted because of the decreased spatial distances between them as a result of shrinkage of the microgels,leading to their plasmonic coupling. The temperature tunable plasmonic coupling is demonstrated by temperature dependence of the surface enhanced Raman spectroscopy( SERS) signal of 1-naphthol in aqueous solution. Different from static plasmonic coupling modes from nanostructured assembly or array system of noble metals,the proposed plasmonic coupling can be dynamically controlled by environmental temperature. Therefore, the thermo responsive hybrid microgels have potential applications in mobile LSPR or SERS microsensors for living tissues or cells.

UV-Vis and Surface Photovoltage Spectra of Fe_2O_3/Polystyrene Composite Microspheres

Fe_2O_3 sol with the particle diameter of 3-5 nm was flocculated by the addition of SDS, and the flocculate formed was redispersed by the further addition of that surfactant. Thus the surfactant bilayer was formed on the surface of Fe_2O_3. The emulsion polymerization of styrene(St) adsolubilized on the surfactant adsorbed bilayer was carried out by initiator potassium persulfate(KPS). The UV-Vis and surface photovoltage spectra(SPS) indicate that the Fe_2O_3 particles were encapsulated in polystyrene(PSt) successfully.

Dexamethasone-Loaded PLGA Microspheres Incorporated PLLA/PLGA/PCL Composite Scaffold for Bone Tissue Engineering

The combination of micro-carriers and polymer scaffolds as promising bone grafts have attracted considerable interest in recent decades.The poly(L-lactic acid)/poly(lactic-co-glycolic acid)/polycaprolactone(PLLA/PLGA/PCL)composite scaffold with porous structure was fabricated by thermally induced phase separation(TIPS).Dexamethasone(DEX)was incorporated into PLGA microspheres and then loaded on the PLLA/PLGA/PCL scaffoldtopreparethedesiredcompositescaffold.The physicochemical properties of the prepared composite scaffold were characterized.The morphology of rat bone marrow mesenchymal stem cells(BMSCs)grown on scaffolds was observed using scanning electron microscope(SEM)and fluorescence microscope.The resultsshowedthatthePLLA/PLGA/PCLscaffoldhad interconnected macropores and biomimetic nanofibrous structure.In addition,DEX can be released from scaffold in a sustained manner.More importantly,DEX loaded composite scaffold can effectively support the proliferation of BMSCs as indicated by fluorescence observation and cell proliferation assay.The results suggested that the prepared PLLA/PLGA/PCL composite scaffold incorporating drug-loaded PLGA microspheres could hold great potential for bone tissue engineering applications.

High-strength Ti-BN composites with core-shell structured matrix and network-woven structured TiB nanowires

A novel architectural Ti composite composed of network-woven structured TiB nanowires in a core-shell structured Ti matrix was fabricated to improve the strength of Ti matrix composites(TMCs),where the shell consists of rich N solute atoms while the core is deficient of N solute atoms through spark plasma sintering of powder mixtures of Ti powder and BN nano-powder.The phase composition,morphology,element distribution,and mechanical properties of prepared samples were analyzed by X-ray diffraction(XRD),scanning electron microscope(SEM),electron probe microanalyzer(EPMA),and electronic universal material testing machine.The results indicate that the TMCs with designed architectures have been successfully achieved,and the as-prepared Ti-2BN(wt.%)composite exhibits an ultimate compressive strength of~1.8 GPa with a strain-to-fracture of~9%,while the Ti-1BN(wt.%)attains an ultimate compressive strength of~1.6 GPa and a strain-to-fracture of~20%.Moreover,the roles of the hybrid reinforcement structures in strengthening the Ti composites were discussed.

Synthesis and Characterization of Cobalt-Carbon Core-Shell Microspheres in Supercritical Carbon Dioxide System

The synthesis of cobalt-carbon core-shell microspheres in supercritical carbon dioxide system was investi- gated. Cobalt-carbon core-shell microspheres with diameter of about 1μm were prepared at 350 ℃ for 12 h in a closed vessel containing an appropriate amount of bis（cyclopentadienyl）cobalt powder and dry ice. Characterization by a variety of techniques, including X-ray powder diffraction, X-ray photoelectron spectroscopy, TransmissiOn electron microscope, Fourier transform infrared spectrum and Raman spectroscopy analysis reveals that each cobalt-carbon core-shell microsphere is made up of an amorphous cobalt core with diameter less than 1 μm and an amorphous carbon shell with thickness of about 200 nm. The possible growth mechanism of cobalt-carbon core-shell microspheres is discussed, based on the pyrolysis of bis（cyclopentadienyl）cobalt in supercritical carbon dioxide and the deposition of carbon or carbon clusters with odd electrons on the surface of magnetic cobalt cores due to magnetic attraction. Magnetic measurements show 141.41 emu/g of saturation magnetization of a typical sample, which is lower than the 168 emu/g of the corresponding metal cobalt bulk material. This is attributed to the considerable mass of the carbon shell and amorphous nature of the magnetic core. Control of magnetism in the cobalt-carbon core-shell microspheres was achieved by annealing treatments.

Fabrication of hierarchical MXene-based AuNPs-containing core-shell nanocomposites for high efficient catalysts

MXene is a new type of layered two-dimensional transition metal carbide materials differing from graphene, demonstrating intriguing chemical/physical properties. Here the chemical modification of MXene and next fabrication of core-shell MXene-COOH@(PEI/PAA)_n composites have been investigated. The obtained MXene-based composites were treated with gold nanoparticles to form MXene—COOH@(PEI/PAA)_n@AuNPs nanocomposites, and their catalytic properties for nitro-compounds were studied. The prepared nanocomposites demonstrated good catalytic activity and reproducibility, showing potential applications in composite catalysts and environmental fields.

Tailoring microstructure and mechanical properties of aluminum matrix composites reinforced with novel Al/CuFe multi-layered core-shell particles

Aluminum matrix composites(AMCs), reinforced with novel pre-synthesized Al/Cu Fe multi-layered coreshell particles, were fabricated by different consolidation techniques to investigate their effect on microstructure and mechanical properties. To synthesize multi-layered Al/Cu Fe core-shell particles, Cu and Fe layers were deposited on Al powder particles by galvanic replacement and electroless plating method, respectively. The core-shell powder and sintered compacts were characterized by using X-ray diffraction(XRD), scanning electron microscopy(SEM) equipped with energy dispersive spectroscopy(EDX), pycnometer, microhardness and compression tests. The results revealed that a higher extent of interfacial reactions, due to the transformation of the deposited layer into intermetallic phases in spark plasma sintered composite, resulted in high relative density(99.26%), microhardness(165 HV0.3) and strength(572 MPa). Further, the presence of un-transformed Cu in the shell structure of hot-pressed composite resulted in the highest fracture strain(20.4%). The obtained results provide stronger implications for tailoring the microstructure of AMCs through selecting appropriate sintering paths to control mechanical properties.

Crystal phase control and ignition properties of HNS/CL-20 composite microspheres prepared by microfluidics combined with emulsification techniques

Improved controllability and energy density of ignition agents are of great significance for the devel-opment of energetic composite materials.In this study,droplet microfluidics and emulsification tech-niques were combined to prepare HNS/CL-20 composite microspheres with polyglycidyl azide polymer(GAP)as the binder.The influence of binder content on the morphology of microspheres was investi-gated,and the microspheres were characterized and tested for particle size,crystal structure,thermal decomposition,dispersibility,mechanical sensitivity,combustion behavior and detonation performance.The results showed that microspheres prepared with a binder content of 3%had higher sphericity and particle size uniformity.The microspheres retained the crystal structure of both HNS and CL-20(ε-type).Compared with raw HNS,the microspheres had higher apparent activation energy,better safety per-formance,and good dispersibility.The ignition experiments and detonation performance tests show that HNS/CL-20 composite microspheres have excellent ignition performance,obvious combustion flame,and significant energy release effects,which are expected to achieve high energy and high-speed response of the igniter,thus improving the ignition reliability in special environments or systems.

Preparation of Dysprosium Ferrite/Polyacrylamide Magnetic Composite Microsphere and Its Characterization

Using the technique of microemulsion polymerization with nano-reactor, dysprosium ferrite/polyacrylamide magnetic composite microsphere was prepared by one-step method in a single inverse microemulsion. The structure, average particle size, morphology of composite microsphere were characterized by FTIR, XRD, TEM and TGA. The magnetic responsibility of composite microsphere was also investigated. The results indicate that the magnetic composite microsphere possess high magnetic responsibility and suspension stability.

A dandelion-like carbon microsphere/MnO_2 nanosheets composite for supercapacitors

This article reported the electrochemical performance of a novel cabon microsphere/MnO2nanosheets(CMS/MnO2) composite prepared by a in situ self-limiting deposition method under hydrothermal condition. The results of scanning electron microscopy(SEM) and transmission electron microscopy(TEM) revealed that MnO2nanosheets homogeneously grew onto the surface of CMS to form a loose-packed and dandelion-like core/shell microstructure. The unique microstructure plays a basic role in electrochemical accessibility of electrolyte to MnO2active material and a fast diffusion rate within the redox phase. The results of cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectrometry indicated that the prepared CMS/MnO2composite presented high capacitance of 181 F g-1and long cycle life of 61% capacity retention after 2000 charge/discharge cycles in 1 mol/L Na2SO4solution, which show strong promise for high-rate electrochemical capacitive energy storage applications.