Thermal and optical properties of polymer hosts for solid-state dye lasers.

We present measurements of thermal and optical properties of poly(methyl methacrylate) (PMMA), PMMA modified by the addition of ethanol (MPMMA), and copolymers of methyl methacrylate with 2-hydroxyethyl methacrylate [P(HEMA:MMA)]. Spectral transmission of the polymers is excellent (alpha = 0.5 cm(-1) at 400 nm, decreasing to 0.04 cm(-1) at 633 nm). Measured laser damage thresholds of MPMMA and P(HEMA:MMA) show at least a twofold increase over PMMA. Thermal lensing measured in these hosts doped with Rhodamine 6G is shown to be similar (f = -450 mm for pump power of 200 mW in a 2-mm-diameter spot, scaling with pump intensity). Compared with MPMMA, P(HEMA:MMA) offers an improved surface quality and a more uniform dye distribution.     

Surface characteristics and blood compatibility of PVDF/PMMA membranes

Poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) membranes have important applications as biomaterials. In this study, PVDF/PMMA with varying ratios is blown into membranes, the surface property and blood compatibility of which are thoroughly investigated. Membrane surface characteristics including composition and topography exert considerable influence on the blood compatibility. Introduction of PMMA disturbs PVDF crystallization, however, favors the β phase crystal formation. PVDF content, crystallization ability, and surface enrichment have decisive effects on the membrane surface composition. Meanwhile, with increased PMMA fraction, the membrane surface roughness is also increased, and subsequently results in decreased hemocompatibility. While the membranes with PMMA content lower than 30 wt% show good blood compatibility, those with higher PMMA fraction exhibit obvious platelet adhesion to the surface. Thermal annealing promotes the formation of β phase PVDF and generates much smoother surface, thus endowing the membranes with greatly enhanced blood compatibility. These results show the prospect for optimization of processability, surface property, and blood compatibility of PVDF/PMMA membranes through facile modulation of PMMA content and fabrication process.     

PP/PMMA接枝剑麻纤维复合材料(Ⅰ)剑麻纤维/MMA接枝聚合反应

用硝酸铈铵作引发剂,将甲基丙烯酸甲酯(MMA)接枝到剑麻纤维(SF)的表面。研究了接枝聚合反应的规律．并考察了接枝聚合对SF热稳定性的影响。结果表明．当反应时间达4h后。单体转化率趋于恒定;MMA与SF质量比在0．85左右。接枝率处于最大值;当引发荆浓度为8mmol／L时,接枝率和接枝效率都比较理想。SF表面接枝聚甲基丙烯酸甲酯(PMMA)导致了SF的原纤化,提高了其抗湿性和热稳定性。     

Electrical and mechanical properties of PMMA/reduced graphene oxide nanocomposites prepared via in situ polymerization

We report the effect of filler incorporation techniques on the electrical and mechanical properties of reduced graphene oxide (RGO)-filled poly(methyl methacrylate) (PMMA) nanocomposites. Composites were prepared by three different techniques, viz. in situ polymerisation of MMA monomer in presence of RGO, bulk polymerization of MMA in presence of PMMA beads/RGO and by in situ polymerization of MMA in presence of RGO followed by sheet casting. In particular, the effect of incorporation of varying amounts (i.e. ranging from 0.1 to 2 % w/w) of RGO on the electrical, thermal, morphological and mechanical properties of PMMA was investigated. The electrical conductivity was found to be critically dependent on the amount of RGO as well as on the method of its incorporation. The electrical conductivity of 2 wt% RGO-loaded PMMA composite was increased by factor of 10⁷, when composites were prepared by in situ polymerization of MMA in the presence of RGO and PMMA beads, whereas, 10⁸ times increase in conductivity was observed at the same RGO content when composites were prepared by casting method. FTIR and Raman spectra suggested the presence of chemical interactions between RGO and PMMA matrix, whereas XRD patterns, SEM and HRTEM studies show that among three methods, the sheet-casting method gives better exfoliation and dispersion of RGO sheets within PMMA matrix. The superior thermal, mechanical and electrical properties of composites prepared by sheet-casting method provided a facile and logical route towards ultimate target of utilizing maximum fraction of intrinsic properties of graphene sheets.     

Plasticity of styrene-co-methylmethacrylate random copolymers

The plastic deformation of styrene-methylmethacrylate random copolymers has been studied as a function of comonomer composition and compared to the behaviour of PS and PMMA homopolymers. Activation parameters derived from a thermodynamic and kinetic analysis of plastic flow reveal the strong influence of the MMA units in controlling the elementary deformation event.     

Fibre-reinforced composite implant: in vitro mechanical interlocking with bone model material and residual monomer analysis

The aim of this study was to examine in vitro the mechanical interlocking of an experimental implant made of E-glass fibre-reinforced polymethyl methacrylate (PMMA)-based composite (FRC) to dental stone. FRC implants with a porous surface were embedded into the dental stone, which was chosen to simulate bone ingrowth into the porous surface of the implant, after which push-out tests were performed. PMMA cylinders with smooth and grooved surface were used as controls. In addition, the release of residual methyl methacrylate monomer (MMA) into water from FRC and control implants with different compositions and fabrication methods was determined using high performance liquid chromatography (HPLC). The highest push-out force (2149 ± 263 N) was measured for the implants with grooved surface and the lowest value for the implants with smooth surface (194 ± 68 N). The push-out forces were over five times higher for FRC implants with a porous surface (958 ± 217 N) than for implants with smooth surface. During the first day of testing, the MMA release into water was 1.4–2.8 times higher from the FRC implants than from the control PMMA implants, depending on fabrication method. With time, the difference between the implants diminished.     

微悬浮法CaCO3表面接枝PMMA及其在PVC中的应用

在水介质中,超声作用下用油酸对纳米碳酸钙进行表面修饰,再以微悬浮原位聚合法用PMM A进行接枝包覆,成功制备了PMM A/C aCO3复合粒子。借助透射电镜(TEM)、红外光谱(FT-IR)、热失重(TG)等分析手段对复合粒子的形态结构进行了表征。实验结果表明,油酸可通过羧酸盐的形式吸附于碳酸钙粒子表面,一定量PMM A通过油酸分子的不饱和双键接枝于碳酸钙粒子表面。将所得PMM A/C aCO3复合粒子与PVC共混制得PVC/PMM A/C aCO3复合材料。复合材料的TEM照片表明,C aCO3粒子非常均匀地分散在PVC基体中,两相界面模糊。随着PMM A/C aCO3纳米复合粒子用量的增加,复合材料的强度和韧性同时提高。当复合粒子用量高于12%时,复合材料的冲击强度可提高3倍,而拉伸强度下降很少。     

Relationship between the morphology of PMMA particles and properties of acrylic bone cements

Bone cements are mainly based on acrylie polymers, poly (methyl methacrylate) (PMMA) being the most representative. The curing process (cold curing) is the result of the free radical polymerization of a mixture of beads of PMMA and methyl methacrylate (MMA), initiated by benzoyl peroxide (BPO) and activated by the presence of a tertiary amine, the most classical being N,N-dimethyl-4-toluidine (DMT). In this work the results on the effect of the size and size distribution of PMMA beads and the concentration of DMT and BPO on the setting parameters, the residual monomer content and the mechanical properties (tension and compression) of the cured systems are presented. The use of relatively larger diameter PMMA beads improves the characteristic parameters of the curing process (decreasing the peak temperature and increasing the setting time), without detrimental effects on the mechanical properties of the cured cement.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials, Oporio, Portugal, 10–13 September.     

软段结构对聚酯型聚氨酯结晶性影响的研究

用３种聚酯二醇ＰＥＡ、ＰＢＡ、ＰＨＡ和ＭＤＩ，以溶液聚合法合成了３个系列的线型嵌段聚氨酯胶粘剂（ＰＥＡＵ、ＰＢＡＵ、ＰＨＡＵ）。以Ｘ－Ｒａｙ衍射法测定了３种聚酯和３个系列聚氨酯的结晶度，讨论了聚酯类型、聚酯分子量、聚氨酯中硬段含量等因素对聚氨酯结晶能力的影响。结果表明，在硬段含量不高（＜２５％）情况下，聚氨酯中的结晶部分主要是由聚酯软段引起的，而聚酯结晶能力大小的次序为ＰＨＡ＞ＰＢＡ＞＞ＰＥＡ，增     

Influence of free volume on the mechanical properties of Epoxy/poly (methylmethacrylate) blends

Positron lifetime measurements have been performed to investigate the free volume dependence of the mechanical properties of Epoxy/poly methyl methacrylate (PMMA) blends of varying composition of PMMA (2.5, 5, 7.5, 10, 12.5, 15, and 17.5 wt%). The mechanical properties of the blends have been evaluated according to the (ASTM) standard. The positron results indicate that the mechanical properties like tensile strength and surface hardness have a significant dependence on the free volume of the blends. It is also found that the blends of the present study show positive deviation from the familiar linear additivity rule suggesting the immiscible nature of the blends. Further, up to 5-wt% of PMMA in the blend, an increase in relative fractional free volume correlates well with a decrease of tensile strength.     

Weak variband surface layers as an effective means of protection from the surface recombination of photoexcited carriers in infrared threshold CdHgTe photoresistors

It is demonstrated that variband near-surface layers with even a small composition gradient can provide ultimate photomodulation (corresponding to the absence of the surface recombination) of the conductivity of thin CdHgTe samples used for manufacturing threshold photoresistors (including those of the SPRITE type) for the wavelengths λ =8−12 μm and λ=3−5 μm. This is explained by the formation (even in weak variband layers) of a special profile of the photoexcited carrier distribution that inhibits their diffusion to the surface. As is known, the introduction of the near-surface variband layers with a small composition gradient must not lead to any substantial increase in the number of defects in the sample.     

Evolution of Near-Surface Elemental Composition Profile and Its Effect on Thermal Diffusivity

In a series of recent experiments, utilizing the method of time resolved spectroscopy of laser-produced plasma (LPP) plumes from specimen surfaces, the near-surface elemental composition profiles were observed to be nonuniform and significantly different from the respective bulk composition. A new study of three alloy systems is reported, with a view toward establishing the causal relationship between the near-surface elemental composition profile of a specimen and its thermophysical properties in general and thermal diffusivity in particular. The systems in question are as follows: two-element Nichrome ribbon; four-element magnetic Mumetal foil; and four-element Wood's alloy. The method of LPP plume spectroscopy has been used throughout to successively expose new surface layers and measure the composition and thermal diffusivity. With two of the systems, modification of the near-surface elemental composition profiles has been forced. Sustained electrical heating of a Nichrome ribbon specimenrevealed preferential diffusion of chromium to the surface, affecting the spectral emissivity and thermal diffusivity as well as depth-dependent local heating rates. In the case of Wood's alloy a sample is melted and re-solidified under a protocol that highlights gravitational forcing. The noncontact spectroscopic method has been used to discover that the top and bottom surfaces acquire two different composition profiles and exhibit commensurate disparity in the measured thermal diffusivity profiles.     

Acrylic-phosphate glasses composites as self-curing controlled delivery systems of antibiotics

New antibiotic delivery systems based on self-hardening methyl methacrylate (MMA)/polymethyl methacrylate (PMMA) systems and phosphate glasses (PG) in the system P₂O₅–CaO–Na₂O have been developed. Self-curing formulations were prepared by mixing the solid component containing PMMA beads, different proportions of PG (30–70 wt %) and vancomycin (5 wt %) as antibiotic, with the liquid component made of MMA monomer. Dough and setting times increased with the content of PG but peak temperature decreased to values well below to guarantee the chemical stability of the antibiotic drug, gentamicin or vancomycin. Mechanical properties of the PMMA/PG composites were evaluated in compression test giving rise to values of compressive strength in the range of 100 MPa. The release of vancomycin was analyzed in vitro by immersion of samples in phosphate buffer of pH=7.4. Release profiles were influenced by the content of PG present in the cement. An initial burst of drug release was observed in all cases. The composites with 70 wt % PG released nearly the total amount of drug loaded in a period of 45 days, and those containing 60 wt % PG released the 70% of the vancomycin in the same period of time. However, either the control of the composite with 30 wt % PG released only the 30% of the drug in 10–15 days. The surface of the drug-loaded composites before and after release experiments was analyzed by ESEM. The deposition of some aggregates at certain points of the surface was detected for the specimens immersed in buffer phosphate after 45 days. This material was characterized by FTIR and Raman spectroscopy as an amorphous phosphate formed by calcium ortho and pyrophosphates, and indicates an interaction between the hydrated layer at the place of the glass and the surrounding medium.     

Dispersion characteristics and properties of poly(methyl methacrylate)/multi-walled carbon nanotubes nanocomposites

The preparation, characterization, and properties of poly(methyl methacrylate) (PMMA)/multi-walled carbon nanotubes (MWCNTs) nanocomposites are described. Nanocomposites have been prepared by melt-blending in a batch mixer. Both unmodified and surface modified MWCNTs have been used for the nanocomposites preparation. Using both unmodified and modified MWCNTs, the effect of surface modification in nanocomposites is investigated by focusing on three major aspects: dispersion characteristics, mechanical properties, and electrical conductivity measurements. Dispersion of the MWCNTs in the PMMA matrix is examined by scanning and transmission electron microscopy that revealed a homogeneous distribution-dispersion of MWCNTs in the PMMA matrix for both unmodified and modified MWCNTs. Thermomechanical behavior is studied by dynamic mechanical analyzer and results showed a substantial improvement in the mechanical properties of PMMA in conjunction to an increase in the elastic behavior. The tensile properties of neat PMMA moderately improved after nanocomposites preparation with both modified and unmodified MWCNTs, however, electrical conductivity of neat PMMA significantly improved after nanocomposites preparation with 2 wt% unmodified MWCNTs. For example, the through plane conductivity increased from 3.6 x 10(-12) S x cm(-1) for neat PMMA to 3.6 x 10(-9) S x cm(-1) for nanocomposite. The various property measurements have been conducted and results have shown that, in overall, surface modifications have very little or no effect on final properties of neat PMMA.     

Radiation-induced grafting of methylmethacrylate onto ultrahigh molecular weight polyethylene and its adhesive characteristics

The surface of ultrahigh molecular weight polyethylene (UHMWPE) was modified by radiation-grafting methylmethacrylate (MMA) in the presence of sulfuric acid and metallic salt to increase bonding strength with polymethylmethacrylate. The effect of the addition of metallic salts and sulfuric acid on the radiation grafting reaction was investigated when MMA was grafted to the irradiated UHMWPE. The adhesive characteristics with the grafting yield were investigated using conventional acrylic bone cement based on poly(methyl methacrylate) [PMMA]. The results showed that the inclusion of an and sulfuric acid in MMA grafting solutions was extremely beneficial and led to a most unusual synergistic effect, while led to a detrimental effect. The tensile bonding strength between UHMWPE and PMMA sheet increased remarkably with an increased grafting yield on UHMWPE surfaces.     

ATRP方法可控合成碳纳米管/PMMA纳米复合材料

通过多壁碳纳米管的表面改性合成了ATRP引发剂,利用合成的ATRP引发剂进行ATRP活性聚合,成功地在碳纳米管表面接枝聚合物PMMA。利用红外(IR)、透射电镜(TEM)、热重(TGA)以及核磁共振(NMR)表征接枝的碳纳米管,考察了碳纳米管用量对碳纳米管/PMMA纳米复合材料力学性能的影响,结果表明,碳纳米管表面成功接枝聚合物PMMA,PMMA的力学性能得到很大改善。     

Depth-profiling of phase composition and preferred orientation in a graded alumina/mullite/aluminium-titanate hybrid using X-ray and synchrotron radiation diffraction

X-ray diffraction (XRD), grazing-incidence synchrotron radiation diffraction (GISRD) and multi-wavelength synchrotron radiation diffraction (MWSRD) have been successfully used for near-surface depth profiling of phase composition and texture in a functionally-graded alumina/mullite/aluminium-titanate hybrid prepared by an infiltration process. Depth profiling of near-surface information both in the nanometer and micrometer scale has been done by (a) varying the X-ray wavelength, (b) varying the grazing-incidence angle, and (c) gradual polishing of the sample surface with diamond lap. Results show a distinct gradation in the phase abundance near the surface of the hybrid sample. The distribution of mullite near the surface is highly textured and shows a distinct depth-dependent gradation in preferred grain-orientation. The unique but powerful capability of XRD, GISRD and MWSRD as complementary tools for depth profiling the near-surface region of graded materials has been demonstrated in this work.     

Hollow microspheres and aqueous phase behavior of pH-responsive poly(methyl methacrylate-co-methacrylic acid) copolymers with a blocky comonomer distribution

Copolymers of methyl methacrylate (MMA) and methacrylic acid (MAA) were prepared by partial hydrolysis of PMMA in bad solvent. These copolymers evidently have a blocky comonomer distribution –strands of predominantly MMA or MAA across the polymer– and show sharp transitions in aqueous solution upon pH change. Additionally, their hollow microcapsules show an exceptional and prolonged stability at acidic conditions (pH 2) and pH-triggered release at physiological conditions.     

Particle monolayer formation with arrayed structure by PMMA-grafted polystyrene Latex at the air-water interface

The structure of the particle monolayer formed by the polymer-grafted latex particle at the air-water interface was estimated mainly by pi--A isotherm measurement and SEM observation to examine the effect of core particle characteristics and to generalize the key factors in determining the polymer-grafted particle monolayer structure. Methyl methacrylate (MMA) was polymerized from the polystyrene latex (PSL) surface by atom transfer radical polymerization to give a PMMA-grafted PSL (PSL-PMMA) with a relatively high graft density of about 0.2 nm-2. We obtained PSL-PMMA with PMMA of different molecular weights but almost the same graft density. The onset area of increasing surface pressure in pi-A isotherm was in agreement with the value of effective radius of PSL-PMMA with quite extended PMMA chains. The particle monolayer structure deposited on the substrate was strongly dependent on the molecular weight of the grafted PMMA. The aggregation size was reduced with increasing molecular weight and a lattice-like structure was observed for PSL-PMMA monolayer with a high molecular weight PMMA. The interparticle distance was decreased and structure becomes ordered with increasing surface pressure. The monolayer structure obtained here was consistent with that of the PMMA-grafted silica particle system. We also synthesized polystyrene (PS)-grafted PMMA latex (PML-PS) and compared the two systems. We confirmed that the lattice-like structure depended on the nature of the grafted PMMA chain, not the core particle characteristics.     

The influence of storage relative humidity on aerosolization of co-spray dried powders of hygroscopic kanamycin with the hydrophobic drug rifampicin

The purpose of this study was to investigate the influence of storage humidity on in vitro aerosolization and physicochemical properties of co-spray dried powders of kanamycin with rifampicin. The powders were stored for one-month in an open Petri dish at different relative humidities (RHs) (15%, 43%, and 75%) and 25?±?2?°C. The in vitro aerosolization (fine particle fraction, FPF) of the powders was determined by a next generation impactor (NGI). The moisture content, particle morphology and crystallinity of the powders were determined by Karl Fischer titration, scanning electron microscopy, and X-ray powder diffractometry, respectively. At all RH, the FPF of hydrophobic rifampicin-only powder was unaffected but the FPF of hygroscopic kanamycin-only powder significantly decreased even at 43% RH. The kanamycin-only particles fused together, crystallized and formed hard cakes at 75% RH. The aerosolization of kanamycin and rifampicin in the combination powders remained unaffected at 15% and 43% RH, but aerosolization significantly decreased at 75% RH. Enrichment of the surface of the particles with hydrophobic rifampicin did not protect the combination powders from moisture uptake but it prevented particle agglomeration up to 43% RH. At 75% RH, the moisture uptake led to agglomeration of the particles of the combination powder particles and consequently an increase in aerodynamic diameter. Further studies are required to investigate how rifampicin enrichment prevents particle agglomeration, the possible mechanisms (e.g. particle interactions due to capillary forces or electrostatic forces) for the changes in the aerosolization and changes in surface composition during storage.