Porous agarose/Gd-hydroxyapatite composite bone fillers with promoted osteogenesis and antibacterial activity

Artificial bone fillers are essentially required for repairing bone defects, and developing the fillers with synergistic biocompatibility and anti-bacterial activity persists as one of the critical challenges. In this work, a new agarose/gadolinium-doped hydroxyapatite filler with three-dimensional porous structures was fabricated. For the composite filler, agarose provides three-dimensional skeleton and endows porosity, workability, and high specific surface area, hydroxyapatite (HA) offers the biocompatibility, and the rare earth element gadolinium (Gd) acts as the antibacterial agent. X-ray photoelectron spectroscopy detection showed the doping of Gd in HA lattice with the formation of Gd-HA interstitial solid solution. Attenuated total reflection Fourier transform infrared spectroscopy imaging suggested chemical interactions between agarose and Gd-HA, and the physical structure of agarose was tuned by the Gd-doped HA. Cytotoxicity testing and alizarin red staining experiments using mouse pro-osteoblasts (MC3T3-E1) revealed remarkable bioactivity and osteogenic properties of the composite fillers, and proliferation and growth rates of the cells increased in proportion to Gd content in the composites. Antibacterial testing using the gram-positive bacteria S. aureus and the gram-negative bacteria E. coli indicated promising antibacterial properties of the fillers. Meanwhile, the antibacterial properties of composite filles were enhanced with the increase of Gd content. The antibacterial fillers with porous structure and excellent physicomechanical properties show inspiring potential for bone defect repair.     

Improved Matrix-Filler Adhesion

Enhanced matrix-filler adhesion is realized after filler treatment with a surface treatment process. The hydrosol/coupling agent treatment was applied to a wide range of inorganic and organic fillers, and adhesion to a variety of matrix resins was improved. Scanning Electron Microscopy (SEM) was used to determine the locus of failure in the filled systems. The locus of failure shows the relative degree of adhesion between the filler and the polymer matrix. Significant improvement in adhesion in humid environments is also observed.     

Preparation of Iron Filler-Based Photocomposites and Application in 3D Printing

The introduction of metallic fillers to polymers via the photopolymerization approach can endow the composite materials with some unique properties, but the relevant research is still scarce due to the issue of light penetration and inner filter effect. Herein, for the first time the fabrication of photocomposites based on fine iron powder (i.e., a typical kind of metallic filler) is reported in this work. The free radical polymerization of two different acrylate monomers, poly(ethylene glycol) diacrylate and trimethylolpropane triacrylate, is performed in the presence of iron filler under mild conditions (i.e., light emitting diode (LED)@405 nm irradiation at room temperature under air). And the real-time Fourier transform infrared spectroscopy reveals remarkable photopolymerization kinetics of acrylates with high final conversions and fast polymerization rates despite the increasing contents of iron filler in the composites. Interestingly, the 3D printing technique is applied to the iron filler-based composites to produce tridimensional patterns with excellent spatial resolution. This work not only paves the way for the investigation of photocomposites based on metallic fillers through photochemical methods, but also broadens the potential application prospects.     

PVC基阻尼涂料的制备及其流变性能

以聚氯乙烯（PVC）为基体，对苯二甲酸二辛酯（DOTP）为增塑剂，与无机填料CaCO3、钙锌热稳定剂、乳化剂OP-10、润滑剂液体石蜡等复合改性制备PVC基阻尼材料，采用动态流变仪DHR、动态热机械分析仪DMA、扫描电镜SEM等对试样的性能和形态进行表征。运用正交设计探究各组分对性能的影响规律，结果表明，填料CaCO3和增塑剂DOTP比例对其阻尼性能影响最显著；当PVC: CaCO3: DOTP: OP-10比重为45: 33: 22: 2时，25℃时频率0.01～150 Hz范围内，tan δ最大值从0.497提高到0.604；剪切速率0.1 s-1时表观黏度为3738 Pa·s，剪切速率150 s-1时表观黏度为2.19 Pa·s，具有优异的抗流挂性与稳定性。通过LASD形态分析构建微观聚集态模型，提出刚性填料团聚-解团聚和聚合物微球变形对流变性能的作用机理，为LASD的持续研究提供技术思路和理论基础。     

Role of heat transfer and thermal conductivity in the crystallization behavior of polypropylene‐containing additives: A phenomenological model

The thermal conductivity of a filler and the thermal conductivity of a composite made from that filler influence the heat‐transfer process during melt processing. The heat‐transfer process from the melt to the mold wall becomes an important factor in developing the skin–core morphology. These aspects were examined in this study. The thermal conductivity of polypropylene–filler composites was estimated with a standard model for various fillers such as calcium carbonate, talc, silica, wollastonite, mica, and carbon fibers. The rate of cooling under given conditions, including the melting temperature, mold wall temperature, mass of the composite, and filler content, was estimated with standard heat‐transfer equations. The time to attain the crystallization temperature for polypropylene was evaluated with a regression method with differential temperature steps. The crystallization curves were experimentally determined for the different fillers, and from them, the induction period for the onset of crystallization was estimated. These observations were correlated with the expected trends from the aforementioned formalism. The excellent fit of the curves showed that in all these cases, the thermal conductivity of the filler and composite played a dominant role in controlling the onset of the crystallization process. However, the nucleation effects became important in the later stages after the crystallization temperature was attained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2994–2999, 2003     

Investigation of the Influence of Fillers on the Properties of Poly(vinyl acetate) Adhesives

The properties of poly(vinyl acetate) compositions prepared as potential wood adhesives were investigated. The paper presents the results of the influence of various kinds of inorganic fillers based on calcium carbonate and alumino-silicate and an organic filler, starch, on the adhesive composition properties. The comparison among rheological behavior of the adhesive dispersions concerning the specific role of fillers were made. Mechanical and relaxation properties of the adhesive films could reveal the effect of filler characteristics on the polymer matrix. The significant influences of particle size distribution and specific surface area on the poly(vinyl acetate) adhesive composition were determined, along with other filler characteristics.     

纳米CaSiO_3填料的制备及其性能表征

以乙醇为溶剂,正硅酸乙酯(TEOS)为胶溶剂,CaCO3为主要试剂,采用溶胶-凝胶(Sol-Gel)技术制备纳米偏硅酸钙(CaSiO3)填料,考察主要工艺参数——初始水凝胶pH值、R值(H2O/TEOS)对粉体形貌、颗粒大小等性质的影响。研究表明:采用溶胶-凝胶法能合成纳米级的CaSiO3填料。     

Tensile modulus modeling of carbon‐filled nylon 6,6 and polycarbonate‐based resins

Electrically and thermally conductive resins can be produced by adding conductive fillers to insulating polymers. Mechanical properties, such as tensile modulus, are also important. This research focused on performing compounding runs followed by injection molding and tensile testing of carbon‐filled nylon 6,6 and polycarbonate‐based resins. The three carbon fillers investigated included an electrically conductive carbon black, synthetic graphite particles, and a milled pitch–based carbon fiber. For each polymer, resins were produced and tested that contained varying amounts of these single‐carbon fillers. In addition, combinations of fillers were investigated by conducting a full 2³ factorial design and a complete replicate in each polymer. These tensile modulus experimental results were then compared to results predicted by several different models. For the composites containing only one filler type, the Nielsen model with the modified Ψ term provided the best prediction of the actual experimental values. For the composites containing more than one filler type, a new parameter, which includes the vibrated bulk density (VBD) of the fillers, was incorporated into the Nielsen model with the modified Ψ term. This model with the new VBD parameter provided the best estimate of experimental tensile modulus for composites containing multiple‐filler types. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1716–1728, 2003     

Influence of grafted polypropylene on the mechanical properties of mineral‐filled polypropylene composites

The purpose of this work was to study how mineral fillers would behave in a polypropylene (PP) matrix when PP modified with maleic anhydride (MA) and/or itaconic acid (IA) was used as a coupling agent in the preparation of mineral‐filled PP composites. The composites were characterized with tensile mechanical measurements and morphological analysis. The optimum amount of the coupling agent to be used to obtain composites with improved mechanical properties was established. The results indicated that these coupling agents enhanced the tensile strength of the composites significantly, and the extent of the coupling effect depended on the nature of the interface that formed. The incorporation of coupling agents enhanced the resistance to deformation of the composite. The behavior of IA‐modified PP as a coupling agent was similar to that of a commercial MA‐modified PP for the filled PP composites. Evidence of improved interfacial bonding was revealed by scanning electron microscopy studies, which examined the surfaces of fractured tensile test specimens; their microstructures confirmed the mechanical results with respect to the observed homogeneous or optimized dispersion of the mineral‐filler phase in these composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2343–2350, 2007     

Effect of coal filler on the properties of soy protein plastics

The influence of ultrafine coal filler (UFC) content on tensile properties, water absorption, and biodegradability of soy protein plastics were investigated. The addition of UFC in the soy protein plastics, with different content of glycerol as a plasticizer, was at different ratio varying from 10:0 to 6:4. Blend sheets of the soy protein composites were prepared by the compression molding processing. The results show that, with 23.08 wt % glycerol, the tensile strength and elongation at break for the soy protein sheet with coal filler (range from 5 to 30 parts) can be enhanced as compared with nonfilled soy protein plastics. Water resistance of the soy protein plastics improves with the increase in UFC content. The derivative thermogravimetry (DTG) curves indicate a double‐stage degradation process for defatted soy flour (SPF), while three‐stage degradation process for soy plastics and the soy protein composites. FT‐IR, XPS, and SEM were applied to study the interfacial interaction between coal macromolecules and soy protein molecules in UFC filled soy protein plastics. The results demonstrated that there is strong interfacial interaction in the soy protein plastics caused by the compression molding processing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3134–3143, 2006