A Practical Model for the Interactions Between Hydrating Portland Cements and Poly-β-Naphthalene Sulfonate Condensate Superplasticizers

The performance of poly-β-naphthalene sulfonate condensate superplasticizer (BNS) as a dispersant for cement in concrete is affected severely by slight differences in the characteristics of the cement. In order to be able to predict these effects, a model for estimating the fluidity of cement paste containing BNS is proposed. This model is based on an assumption that the fluidity of cement paste is proportional to the BNS adsorption amount per surface area of hydrated cement (Ad/Hy). BNS is known to show two types of sorption on hydrated cement: one is the bulk absorption into initial hydrates and the other one is the superficial adsorption onto hydrates. Only the superficially adsorbed BNS is expected to work as a dispersant. By assuming a competitive Langmuir-type adsorption on hydrates between BNS and SO₄²⁻, a simple method to estimate Ad/Hy is developed, with the concentrations of BNS and SO₄²⁻ as the only two independent parameters. The resulting estimates of Ad/Hy show a good correlation with paste flow and its change with elapsed time for a broad range of cements. The SO₄²⁻ concentration in the aqueous phase of the cement paste just after the beginning of the mixing is known to affect the performance of BNS as a dispersant. By using the proposed model to discriminate between the superficial adsorption and bulk absorption of BNS, this phenomenon is explained quantitatively.     

Dynamic moduli for short fiber-CR composites

The dynamic moduli, E′ and E″, and tan δ for nylon–CR and PET–CR composites with unidirectional short fibers were studied as a function of temperature by using a Rheovibron. The temperature dependence of tan δ showed two dispersion peaks for nylon–CR composite. The peak at ?28°C corresponded to the main dispersion of CR and the peak at 100°C to the α-dispersion of nylon 6. For a PET-CR composite, in addition to the individual dispersion of CR and PET, a small and broad peak was observed at about 90°C. The angular dependence of E′ indicated that the short fibers assumed good orientation. The storage modulus for the composites was given by the parallel model as E′ = V_f′E_f + V_mE′_m., where E′_c, E′_f and E′_m were the storage modulus for the composite, fiber, and matrix and V_f and V_m were the volume fraction of fiber and matrix, respectively. In the transverse direction of fiber, the peak values of tan δ at ?28°C were given by the following equation; tan δ_c = tan δ_m ? δV_f, where tan δ_c and tan δ_m are the loss tangent for the composite and matrix, respectively, and α is coefficient depending on fiber type. The results indicated that a region with strong interaction was formed between fibers and CR matrix.     

An ergonomics study of thumb movements on smartphone touch screen

This study investigated the relationships between thumb muscle activity and thumb operating tasks on a smartphone touch screen with one-hand posture. Six muscles in the right thumb and forearm were targeted in this study, namely adductor pollicis, flexor pollicis brevis, abductor pollicis brevis (APB), abductor pollicis longus, first dorsal interosseous (FDI) and extensor digitorum. The performance measures showed that the thumb developed fatigue rapidly when tapping on smaller buttons (diameter: 9 mm compared with 3 mm), and moved more slowly in flexion–extension than in adduction–abduction orientation. Meanwhile, the electromyography and perceived exertion values of FDI significantly increased in small button and flexion–extension tasks, while those of APB were greater in the adduction–abduction task. This study reveals that muscle effort among thumb muscles on a touch screen smartphone varies according to the task, and suggests that the use of small touch buttons should be minimised for better thumb performance.     

Preparation and properties of graft and block copolymers of poly(p-phenylene terephthalamide) with polybutadiene

Graft copolymers of polybutadiene (PBD) onto poly(p-phenylene terephthalamide) (PPTA) were prepared by the nucleophilic substitution of N-metalated PPTA with telechelic PBD having bromide end groups. Block copolymers were synthesized by the condensation reaction of telechelic PBD having acid chloride end groups with amino-group-terminated PPTA. The structure of these copolymers was identified by IR spectra. Graft and block copolymers contained PBD segments up to 85 wt % and 45 wt %, respectively. Thermomechanical analyses (TMA) proved the existence of distinctive primary absorption peak corresponding with T_g of PBD for both graft and block copolymers. The T_g's of both types of the copolymers were further ascertained by the DSC curves. TMA curves suggested that the microphase separation occurred between PPTA and PBD. The incorporation of PPTA segments into PBD increased the decomposition temperature compared with the blend polymer composed of PPTA and PBD with the same composition.     

Electrochemical reduction of nitrate on Pt(S)[n(1 1 1) × (1 1 1)] electrodes in perchloric acid solution

The electrochemical reduction of nitrate ion was studied by cyclic voltammetry on Pt(1 1 1) and [n(1 1 1) × (1 1 1)] stepped Pt surfaces, where n (=14, 10, 7, 6, 5, 4, 3, 2) is the number of terrace atoms, in 0.1 M HClO₄ + 10 mM KNO₃. The electrocatalytic nitrate reduction was found to hardly proceed on Pt(1 1 1) in the hydrogen adsorption region, while the electrocatalytic activity was improved with the increase in the step density. Inactivation was observed in the presence of adsorbed hydrogen or nitrate-derived reduced adsorbate, i.e. adsorbed NO, on (1 1 1) step sites. It was, therefore, concluded that the electrocatalytically active NO₃⁻ species does not adsorb on the (1 1 1) terraces but on the (1 1 1) monoatomic steps. The nitrate reduction current increased with the step density in a non-linear relationship. The overall current density at 0.21 V (RHE) corresponding to the peak potential of the main electrocatalytic nitrate reduction wave which was maximum at n = 2, abruptly increased with short terraces, i.e. n < 5, where the current wave of adsorbed hydrogen on the Pt stepped surface with comparatively narrow (1 1 1) terraces, denoted as H_nt, also appeared unmodified for n < 5 on voltammograms recorded in 0.1 M HClO₄ in the absence of nitrate.     

Mechanical Properties of Alumina/Silicon Carbide Whisker Composites

The improvement of mechanical properties of Al₂O₃/SiC whisker composites has been studied with emphasis on the effects of the whisker content and of the hot-pressing temperature. Mechanical properties such as fracture toughness and fracture strength increased with increasing whisker content up to 40 wt%. In the case of the high SiC whisker content of 40 wt%, fracture toughness of the sample hot-pressed at 1900° decreased significantly, in spite of densification, compared with one hot-pressed at 1850°. Fracture toughness strongly depended on the microstructure, especially the distribution of SiC whiskers rather than the grain size of the Al₂O₃ matrix.     

New method for selective growth of diamonds by microwave plasma chemical vapour deposition

Selective nucleation and deposition of diamonds were achieved on an SiO₂-patterned Si substrate. The substrate was pre-treated with an electric field in plasma to introduce diamond nuclei. This treatment did not affect the SiO₂ area. Consequently, diamonds grew only on the area where Si was exposed under the conventional conditions of diamond growth. The maximum nucleation density on the area of SiO₂was about 5 × 10⁷ cm⁻². The ratio of the selectivity was 2 × 10² or higher. This process will be useful and very promising for manufacturing diamond electronic devices.     

Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.     

Physical properties of silk fibers treated with ethylene glycol diglycidyl ether by the pad/batch method

This paper deals with the epoxide treatment of silk fabrics by the pad/batch method. The optimum reaction conditions, i.e., NaOH concentration, and reaction temperature were 2.5 g/L and 30°C, respectively. A weight gain of 8.5% was attained at a reaction time of 6 h. This value slightly increased to 10% after 24 h. The reactivity of tyrosine and basic amino acid residues was dependent on the reaction time and did not significantly differ from the results of epoxide-treated silk fiber by the conventional method in tetrachloroethylene. The moisture regain slightly decreased at 4% weight gain and then increased with the epoxide content, exceeding the value of the untreated control. The crease recovery of the epoxide-treated silk fabrics measured in the wet state was significantly improved, whereas that in the dry state was almost unchanged. The rate of photoyellowing of the epoxide-treated silk fabrics by the pad/batch method was reduced significantly compared with that of the untreated control. Among the mechanical properties, elongation at break and tensile modulus remained unchanged, whereas the tensile strength slightly increased following the epoxide reaction. The thermal properties were evaluated by DSC and TGA and on the basis of the dynamic viscoelastic measurements. The DSC curve of the epoxide-treated sample showed a slight increase of the decomposition temperature of silk fibroin. The rate of weight loss determined by TGA remained unchanged regardless of the chemical modification, whereas the peak of loss modulus became broader and shifted to lower temperature. The X-ray diffractograms showed that the crystalline structure of silk fibers was not affected by the reaction with epoxides. © 1993 John Wiley & Sons, Inc.