Multi‐Parameter Study of Nanoscale TiO2 and CeO2 Additives in Composite AP/HTPB Solid Propellants

A statistical Taguchi L8 matrix was used to conduct a multi‐parameter study of the use of nanoscale additives in composite solid propellants. The additives studied were TiO₂ (titania) and CeO₂ (ceria). The other parameters involved in the experiment were the oxidizer loading and distribution, additive percentage and size, additive size (nano‐scale or μm‐scale), and the mixing method. Four baseline propellants without additives were also produced for comparison. The propellants were tested from 3.45 to 13.78 MPa in a strand bomb, and burning rate curves were determined for all formulas. By analyzing the Taguchi matrix, the sensitivity of each parameter according to the pressure sensitivity and burning rate of the propellant was calculated. The dominant factors depend on whether the additive is needed for modifying the pressure index or the absolute value of the burning rate. In general, the effectiveness of the additives was most influenced by oxidizer percentage, oxidizer size distribution, and additive type. The amount of additive, mixing method, and additive size all had relatively minor impacts on the effectiveness of the additives.     

The role of a novel p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene interfacial modifier in polypropylene/mica composites as evidenced by tensile properties

Present work is devoted to the study of the tensile behavior of polypropylene (PP)/mica composites with improved interfacial interactions from the matrix side caused by the presence of a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene (aPP‐pPBM) as an interfacial agent. Hence, aPP‐pPBM was previously obtained, in our laboratories, by reactive processing in the melt of a by‐product (atactic PP) from industrial polymerization reactors. Present article is two‐fold, on one hand it has been planned to evidence the so called interfacial effects caused by this novel interfacial agent (aPP‐pPBM) yielding better final properties of the heterogeneous system as a whole as revealed by tensile mechanical properties, and on the other to obtain models to forecast the overall behavior of the system. For such purpose, a Box‐Wilson experimental design considering the amount of mica particles and of interfacial agent as independent variables was used to obtain polynomials to forecast the behavior of the PP/Mica system in the experimental space scanned. The existence of a critical amount of aPP‐pPBM to optimize mechanical properties appears to emerge. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,microstructure and mechanical properties of Cr2AlC/Al2O3 in situ composites by reactive hot pressing

Al₂O₃ particle-reinforced Cr₂AlC in situ composites were successfully fabricated from powder mixtures of Cr₃C₂, Cr, Al, and Cr₂O₃ by a reactive hot-pressing method at 1400 °C. A possible synthesis mechanism was proposed to explain the formation of the composites in which Al₂O₃ was formed by the aluminothermic reaction between Al and Cr₂O₃, meanwhile, Cr₃C₂, Al, together with Cr reacted to form Cr₂AlC in a shortened reaction route. The effect of Al₂O₃ addition on the microstructure and mechanical properties of Cr₂AlC/Al₂O₃ composites was investigated. The results indicated that the as-sintered products consisted of Cr₂AlC matrix and Al₂O₃ reinforcement, and the in situ formed fine Al₂O₃ particles dispersed at the matrix grain boundaries. The flexural strength and Vickers hardness of the composites increased gradually with increasing Al₂O₃ content. But the fracture toughness peaked at 6.0 MPa m^1/2 when the Al₂O₃ content reached 11 vol.%. The strengthening and toughening mechanism was also discussed.     

Application of the BAMO‐AMMO Alternative Block Energetic Thermoplastic Elastomer in Composite Propellant

A BAMO‐AMMO alternative block (BAAB)‐based thermoplastic composite propellant with 80 % solid content was prepared using BAAB energetic thermoplastic elastomer (ETPE) as the binder, and the formulation was optimized through energy calculation. The densities, heats of explosion, glass‐transition temperatures, and mechanical properties of the samples were determined by surface tension measurements, oxygen bomb calorimetry, differential scanning calorimetry and static tensile tests, respectively. The results showed that this composite propellant can reach a standard theoretical specific impulse of 275.45 s (10 MPa), a density of 1.8102 g cm⁻³, a heat of explosion of 6256 kJ kg⁻¹, a T_g of −50.46 °C, a tensile strength of 1.56 MPa and an elongation at break of 20 %, thus presenting a superior comprehensive property to BAMO‐AMMO random block (BARB)‐based thermoplastic composite propellant.     

Mechanical properties up to 1900 K of Al2O3/Er3Al5O12/ZrO2 eutectic ceramics grown by the laser floating zone method

Directionally solidified Al₂O₃–Er₃Al₅O₁₂–ZrO₂ eutectic rods were processed using the laser floating zone method at growth rates of 25, 350 and 750 mm/h to obtain microstructures with different domain size. The mechanical properties were investigated as a function of the processing rate. The hardness, ∼15.6 GPa, and the fracture toughness, ∼4 MPa m^1/2, obtained from Vickers indentation at room temperature were practically independent of the size of the eutectic phases. However, the flexural strength increased as the domain size decreased, reaching outstanding strength values close to 3 GPa in the samples grown at 750 mm/h. A high retention of the flexural strength was observed up to 1500 K in the materials processed at 25 and 350 mm/h, while superplastic behaviour was observed at 1700 K in the eutectic rods solidified at the highest rate of 750 mm/h.     

Synthesis and mechanical properties of high impact polystyrene with in situ bulk polymerization toughened by one‐pot Nd‐based styrene–isoprene–butadiene terpolymer rubber

High impact polystyrene (HIPS) resins were obtained with in situ bulk polymerization toughened by styrene–isoprene–butadiene terpolymer rubber (SIBR). SIBR prepolymer was prepared through selective polymerization of styrene (St), isoprene (Ip), and butadiene (Bd) in St with [Nd]/[Al]/[Cl] catalyst. Nd‐based catalyst exhibited more favorable activity toward conjugated diene other than St, resulting in St solution of random SIBR with high cis‐1,4 stereoregularity and low St content, which was directly exposed to the free radical polymerization of St to generate HIPS. Effect of toughened rubber and the initiators [difunctional (D2) and trifunctional (T3)] were examined to attain HIPS possessing mechanical properties as follow: impact strength, 0.9–24.8 kJ/m²; tensile strength, 16.0–27.5 MPa; and elongation at break, 7.4–107.0%. Increasing SIBR matrix in HIPS improved the impact strength and decreased tensile strength. The fracture surface morphologies of HIPS specimens were studied by notched impact tests and scanning electron microscopy (SEM), illustrating that the incremental SIBR matrix presented synergistic toughening effect of crazing to enhance the ductile fracture behavior. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43979.     

In‐depth characterization of granular starch‐graft‐polyester compositions as obtained by in situ polymerization of lactones from the starch surface

The synthesis of poly(ε‐caprolactone) (PCL)‐grafted granular starch was carried out either in bulk (without solvent) or in toluene suspension by a two‐step procedure. First step relied upon the activation of the hydroxyl groups available at the starch surface by alkylaluminum derivatives like AlEt₃ and removal of non‐surface‐grafted organo‐aluminum active species. The latter species were made free in solution by reaction with the remaining water molecules still contaminating the polymerization medium despite intensive drying of the starch granules. In the second step, ε‐caprolactone was polymerized via a coordination‐insertion ring‐opening polymerization as initiated by the surface‐grafted aluminum alkoxide species. The present contribution aims at investigating various parameters such as nature of the alkyl aluminum activator and monomer (δ‐valerolactone was studied as well), temperature, concentration, and addition of a solvent (polymerization in toluene suspension), reaction time, and also the experimental procedure used to recover the polyester chains and measure the grafting efficiency. It turns out that, under the studied conditions, dialkylaluminum alkoxides surface‐grafted onto the starch granules were more likely generated and promote a fast polymerization reaction with the formation of grafted PCL chains with a molecular weight that can be as high as 225 000 (M_n value) for polymerization carried out in toluene suspension. Copyright © 2004 Society of Chemical Industry     

Investigation on the melt spinning fibers of PP/organoclay nanocomposites prepared by in‐situ polymerization

Fibers prepared by melt spinning process from the PP (polypropylene)/organoclay nanocomposite were characterized in details with the aid of SEM, FTIR, XRD, DSC, and mechanical measurements. The results suggested that the lower content of organoclay (0.1%) added to the PP matrix increased the crystallinity and mechanical property (tensile strength) of the PP/organoclay nanocomposite fiber. With increasing the content of organoclay (≥ 0.3%), the crystallinity and the tensile strength both a little decreased, and the fiber containing organoclay exhibited multi‐peaks at the same draw ratio during the heating process. Furthermore, the degree of orientation of the fiber increased a little with lower content of organoclay (0.1%) introduction to PP during the infrared dichroism measurement. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The improvement of mechanical properties of SiC/SiC composites by in situ introducing vertically aligned carbon nanotubes on the PyC interface

In order to improve the mechanical properties, vertically aligned carbon nanotubes (VACNTs) were in situ introduced on the pyrocarbon (PyC) interfaces of the multilayer preform via chemical vapor deposition (CVD) process under tailored parameters. Chemical vapor infiltration (CVI) process was then employed to densify the multilayer preform to acquire SiC/SiC composites. The results show that the growth of VACNTs on PyC interface is highly dependent to the deposition temperature, time and constituent of gas during CVD process. The preferred orientation and high graphitization of VACNTs were obtained when temperature is 800?℃ and C₂H₄/H₂ ratio is 1:3. The bending strength and fracture toughness of SiC/SiC composites with PyC and PyC-VACNTs interfaces were compared. Compared to the SiC/SiC composite with PyC interface, the bending strength and fracture toughness increase 1.298 and 1.359 times, respectively after the introduction of PyC-VACNTs interface to the SiC/SiC composites. It is also demonstrated that the modification of PyC interface with VACNTs enhances the mechanical properties of SiC/SiC composites due to the occurrence of more fiber pull-outs, interfacial debonding, crack branching and deflection     

Investigation of the extraction process in gel‐spinning technology for ultrahigh‐molecular‐weight polyethylene fibers by low‐field nuclear magnetic resonance

A portable, low‐field nuclear magnetic resonance scanner, the nuclear magnetic resonance mobile universal surface explorer, is introduced as a tool for investigating the extraction process of mineral oil in the gel‐spinning technology of ultrahigh‐molecular‐weight polyethylene (UHMWPE) fibers. Factors affecting the extraction process were studied systematically; these included the UHMWPE type, extraction agent type, and concentration and ultrasound. We found that the extraction process could be described by a replacement–dilution dual‐effect model. The extraction agent not only replaced and extracted the mineral oil but also considerably decreased the viscosity of mineral oil and thus enhanced the molecular motion and diffusion of mineral oil. Although chloroform had a smaller molecular size and lower boiling point, benzene and cyclohexane were found to exhibit more efficient extraction and dilution effects on mineral oil. The extraction efficiency could be characterized by the diffusion of mineral oil in the mineral oil/UHMWPE gel/deuterated extraction agent multicomponent systems during the extraction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42018.     

The majority of minerals present in natural rubber are associated with the macrogel: An ICP‐MS and SEM/EDX investigation

The mineral composition of the insoluble (macrogel) and soluble fractions of two natural rubber (NR) samples made from the latex of two different clones (RRIM600 from Thailand and GT1 from Côte d'Ivoire) was determined using inductively coupled plasma mass spectrometry (ICP‐MS). The ICP‐MS results showed that mineral elements were concentrated in the macrogel. The major mineral elements found in macrogel were phosphorus, magnesium, potassium, and sulfur. Some mineral elements were mostly concentrated in micron‐sized mineral aggregates, visible at the surface of the samples using scanning electron microscopy coupled with an energy dispersive X‐ray microanalyzer (SEM/EDX). The nature of these mineral aggregates was found to be highly variable. Their inhomogeneous distribution in the macrogel indicates that these aggregates do not have a major influence on macrogel structure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43062.     

Physical and mechanical properties of Al(OH)3/polypropylene composites modified by in situ‐functionalized polypropylene

Al(OH)₃/polypropylene (PP) composites modified by in situ‐functionalized polypropylene (FPP) were prepared by a one‐step melt‐extrusion process. The effect of in situ FPP on the crystallization and melting behavior, melt‐flow index, limiting oxygen index, thermal degradation, mechanical properties, and fracture morphology of Al(OH)₃/PP composites was studied. Formation of in situ FPP resulted in a decreased crystallization temperature and melting point of PP in the composites, an increased melt‐flow index, and improved tensile and flexural strengths of Al(OH)₃/PP composites, whereas the thermal degradation behavior and limiting oxygen index was not been influenced. The impact strength of the Al(OH)₃/PP composites modified by in situ FPP depended upon the content of the initiator, dicumyl peroxide, and the monomer, acrylic acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2850–2857, 2002; DOI 10.1002/app.10269     

An Investigation of Structure–Property Relationships in Silicone‐Based Dielectric Electroactive Elastomers by Varying Stoichiometric Imbalance of the Network

Silicone‐based elastomers are promising materials for future dielectric elastomer actuators. To ensure optimum performance and the long‐term reliability of the actuators, it is essential to gain a fundamental understanding of the correlation between the elastomer's network structure and the mechanical and electrical responses of the material. For this purpose, mechanical and electrical tests are performed on a series of silicone elastomer films with different crosslinking densities, which are prepared by changing the stoichiometric imbalance of the network. It is determined that higher cross‐linking density leads to a higher elastic modulus and a longer fatigue lifetime, whereas reduced permittivity is observed because of lower chain mobility. Dielectric breakdown strength is also observed to increase in line with increasing cross‐linking density, and the variations in relation to the measured elastic modulus and permittivity agree well with the Stark–Garton model based on electromechanical instability.

     

Investigation of the electropolymerization of o‐toluidine and p‐phenylenediamine and their electrocopolymerization by in situ ultraviolet–visible spectroelectrochemistry

Under the conditions of potentiostatic electrolysis, the electropolymerization of o‐toluidine (OT) and para‐phenylenediamine (PPDA) and the electrocopolymerization between OT and PPDA on an indium tin oxide (ITO) conductive glass electrode at potentials of 0.7, 0.8, and 0.9 V were studied in detail by in situ ultraviolet–visible (UV–vis) spectrometry in 0.5 mol/L sulfuric acid media. It was shown that both OT and PPDA could be electropolymerized on the ITO electrode, which depended on the applied electrolysis potential and the concentration of the monomer. Furthermore, in situ UV–vis spectra indicated that the electrocopolymerization between OT and PPDA could happen. The presence of PPDA not only promoted polymerization but also accelerated polymerization, which was attributed to the formation of an intermediate result from the coupling of PPDA and the toluidine monomer cation radical. PPDA could be incorporated into the copolymer to make the copolymer have a phenazine or phenazine‐like cyclic structure, which was proven by the reflectance Fourier transform infrared spectra of the polymer and copolymer. The scanning electron microscopy morphology images of the polymers obtained showed that, in addition to accelerating polymerization, PPDA also could change the method of nucleation for the polymer to make the copolymer possess a fibrous surface morphology. The diameter of the fibroid copolymer was about 100 nm, and the length of that reached about 1000 nm. In the article, a newer concerned mechanism of copolymerization was proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties and morphology of bioceramics/poly(D,L‐lactide) composites modified by in situ compatibilizing extrusion

Composites of poly(D ,L ‐lactide) (PDLLA) with hydroxylapatite (HA) and PDLLA with tertiary calcium phosphate (TCP) were prepared by in situ modification with methylenediphenyl diisocyanate (MDI) and molded by piston extrusion at temperature between T_g and T_m of PDLLA. Mechanical properties of the composites increased obviously when compared with the unmodified bioactive ceramic particles/PDLLA composites. The effect of MDI contents on mechanical properties of the composites was studied. At the optimum conditions of 1.0/1.0molar ratios of ? NCO groups in MDI to ? OH groups in PDLLA, bending strength 68.4 MPa and bending modulus 2281.5 MPa, were achieved in composite HA/PDLLA/MDI with 15 wt % HA. Both increased by nearly 30% when compared with that of solution cast HA/PDLLA composites. Interfacial adhesion and compatibility between PDLLA and bioactive ceramic particles (HA and TCP) were investigated. Scanning electron microscopy (SEM) indicated that the interface between HA particles and PDLLA was blurred and HA particles were closely surrounded by PDLLA matrix in HA/PDLLA/MDI composites. Oriented fibrils along with longitudinal direction of extrusion die were also observed on the surfaces of HA/PDLLA/MDI composite. It is confirmed that MDI has improved interfacial adhesion and compatibility between HA particles and PDLLA phase. Fibril structures formed in the extrusion, and it contributed a great deal in enhancing the mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4085–4091, 2006     

Toughening of a high‐temperature polymer by the sol–gel,in situ generation of a rubbery silica–siloxane phase

A phenyl ether phenyl phosphate polymer, specifically poly(biphenyl ether triphenyl phosphate), was modified to increase its tractability and to improve its toughness. The first goal was achieved by increasing its solubility by sulfonation of the chain, and the second, by the in situ generation of a rubbery phase. This phase was generated by a modification of the usual sol–gel reaction (which usually generates a hard silicalike material by the hydrolysis of a tetrafunctional organosilicate). In this case, a difunctional silicate was included, thus introducing some softening organic groups into the dispersed phase. A bonding agent, N,N‐diethylaminopropyltrimethoxysilane, was also included to improve the bonding between the two phases in this organic–inorganic composite. As expected, the glass transition temperatures generally increased slightly upon sulfonation, but decreased significantly upon introduction of the rubbery phase. Most important, the toughness of the polymer was successfully increased with, for example, only 8 wt % of the rubbery phase, quadrupling extensibility to 20 % and markedly increasing the toughness. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2326–2330, 2001     

Enhancement of radiation‐resistant effect in ethylene–vinyl acetate copolymers by the formation of ethylene–vinyl acetate copolymers/clay nanocomposites

Ethylene–vinyl acetate (EVA) copolymers/clay nanocomposites, prepared by using nonreactive organophilic clay and reactive organophilic clay, were characterized by X‐ray diffraction and by high‐resolution transmission electron microscopy. The influence of gamma irradiation on the structure and properties of the pure EVA and EVA/clay nanocomposites was systematically investigated. In the presence of gamma radiation, the clay can effectively restrain the increase of the storage modulus of EVA/clay nanocomposites, which was supported by dynamical mechanical analysis. Gamma irradiation had almost no effect on the thermal properties of EVA/clay nanocomposites by using nonreactive organophilic clay, but it obviously improved the thermal stability of EVA/clay nanocomposites by using reactive organophilic clay. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2532–2538, 2005     

Structural parameters in relation to the rheological behavior and properties of PP/EPR in‐reactor alloy synthesized by multi‐stage sequential polymerization

The morphology and molecular structure of an in‐reactor polypropylene/ethylene propylene rubber alloy, synthesized by multi‐stage sequential polymerization, were studied with respect to the rheological behavior and final properties of the alloy. The polymer alloys, based on different structural morphologies, were characterized by SEM, GPC, ¹³C NMR, DSC, rheological analysis, and mechanical testing. The scanning electron microscopy of samples showed that the size of the dispersed phase particles is decreased as the switch frequency of copolymerization timing is increased. The GPC results showed that switch frequency slightly altered the molecular weight distribution of the copolymer although it had no effect on PP homopolymer. ¹³C NMR results were used for the evaluation of compatibility between the two phases with changes in switch frequency. DSC results showed that T_m and T_c were almost independent of switch frequency, even though the size of dispersed phase was decreased and the blend crystal content increased with ΔH of about 13%. The small amplitude oscillation rheometry showed that storage modulus and viscosity shifted to higher values when switch frequency increased. In studying the mechanical properties it was revealed that, especially the impact strength increased by about 62% when the size of the dispersed particles was decreased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the preparation and properties of UV‐blocking fabrics of a PET/TiO2 nanocomposite prepared by in situ polycondensation

Poly(ethylene phthalate) (PET)/nano‐TiO₂ composites prepared via in situ polymerization were spun into fiber by the melt‐spinning process. The dispersion of nanosized rutile TiO₂ in the PET was studied using transmission electron microscopy (TEM) and scanning probe microscopy (SPM) techniques. The mechanical properties and the properties of ultraviolet (UV) protection were investigated. The results showed that rutile TiO₂ can be dispersed uniformly by the in situ polycondensation process. The mechanical properties of PET/TiO₂ fiber were slightly affected by adding nano‐TiO₂. The UV‐ray transmittance of PET/nano‐TiO₂ fabrics was below 10% in the UV‐A band and below 1% in the UV‐B band. And the ultraviolet protection factor (UPF) of PET/nano‐TiO₂ fabrics was greater than 50. All these PET/TiO₂ nanocomposite fabrics exhibited excellent UV‐blocking properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1588–1593, 2006