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1.
Changes in density and surface tension of water in silica pores 总被引:3,自引:0,他引:3
T. Takei K. Mukasa M. Kofuji M. Fuji T. Watanabe M. Chikazawa T. Kanazawa 《Colloid and polymer science》2000,278(5):475-480
The density and surface tension of water in small pores of silicas have been investigated. These physical properties of water
in the pores were calculated from a comparison of pore volumes and pore radii which were estimated from adsorption and desorption
isotherms of nitrogen and water. Below a pore radius of about 5 nm both the density and the surface tension of water in the
pores were smaller than those of the bulk liquid and decreased with a decrease in pore size. The density of water in the pores
decreased with an increase in the concentration of surface hydroxyl groups. Similarly the surface tension of water in the
pores is influenced by the surface hydroxyl groups. Anomalous changes in the density and surface tension of the water in the
pores are attributed to the interaction of water molecules with surface hydroxyl groups and hydrogen-bond formation among
water molecules.
Received: 20 April 1999 Accepted in revised form: 17 November 1999 相似文献
2.
Hydrophilic graphite oxide (GO) of lamellar structure was prepared by oxidation of graphite; the thickness of the individual
lamellae was 6.1 Å. GO was hydrophobized by n-alkylammonium cations, and the GO-organocomplex nanocomposites were swollen in organic solvents of various polarities (ethanol,
toluene, cyclohexane, n-heptane) and their binary mixtures. The binary liquid composition determined the size (15–45 Å) of the lamellar GO nanostructures.
Interlamellar swelling was quantitatively characterized by XRD experiments, determination of liquid sorption excess isotherms
and flow microcalorimetry.
Received: 12 November 1997 Accepted: 12 February 1998 相似文献
3.
P. C. Schulz R. M. Minardi M. E. Gschaider de Ferreira B. Vuano 《Colloid and polymer science》1998,276(1):52-58
The air/water interface of the system n-dodecanephosphonic acid (H2DP)–water was studied by surface tension, ion-selective electrodes and evaporation in an electrobalance. The combination of
surface tension and ion-selective electrodes measurements enables to study the adsorption of soluble surfactants above the
cmc using the Gibbs’ equation. H2DP formed a nonideal monolayer at the air/water interface with A
molec=0.995 nm2 below the cmc. Above the cmc there was a reduction in adsorption giving A
molec=6.32 nm2, which remained almost constant in the explored concentration range. This adsorption reduction may be due to a change composition
on micellization, or to a thermodynamic advantage of micellization on adsorption. The reduction in the evaporation rate of
water was mainly due to the reduction of the water activity, caused by the presence of solutes in bulk. This is because the
strong changes in the surface coverage did not have significant influence on the evaporation rate.
Received: 6 January 1997 Accepted: 15 August 1997 相似文献
4.
P. C. Schulz M. A. Morini M. E. Gschaider de Ferreira 《Colloid and polymer science》1998,276(3):232-238
The system dodecyltrimethylammonium hydroxide (DTAOH)–water was studied by surface tension, ion-selective electrodes and
evaporation in an electrobalance. Results confirmed earlier conclusions about a stepwise aggregation mechanism in DTAOH solutions.
The aggregation process started at a total concentration C
T=(2.51±0.10)×10-4 mol dm-3) which probably corresponds to the formation of dimers. At C
T= (1.300±0.041)×10-3 mol dm-3 there was a change in the surface and evaporation behavior, corresponding to the formation of small, fully ionized aggregates
which grew with increasing concentration. At C
T= (1.108±0.010)×10-2 mol dm-3 the formation of true micelles with hydroxide counterions in the Stern layer did not change significantly the evaporation
and adsorption behavior. This means that between this concentration and C
T=(3.02±0.28)× M28.8n10-2 mol dm-3, the changes in structure were gradual. At the latter concentration there was a sudden change in the monolayer state at the
air/water interface, with a strong surfactant desorption, and a major change in evaporation behavior. The changes are compatible
with the formation of few, large aggregates reducing the total concentration of kinetically independent solute units, which
in turn increased the activity of the solvent. This phenomenon is in agreement with literature information. The reduction
in the evaporation rate of water was mainly due to the reduction of the water activity, caused by colligative effects. The
reduction of the effective area available for evaporation had only a slight effect in water evaporation.
Received: 9 January 1997 Accepted: 19 October 1997 相似文献
5.
Hydrophobic layered double hydroxides (LDHs): Selective adsorbents for liquid mixtures 总被引:1,自引:0,他引:1
The external and internal surface area of the calcium aluminum double hydroxide [Ca2Al(OH)6] NO3 ⋅ 2H2O were hydrophobized by the anionic surfactants sodium dodecylsulfate and sodium dodecyl-benzene sulfonate. The adsorption
behavior towards liquid mixtures (benzene/n-heptane and n-propanol/ toluene) was studied by determining the surface excess adsorption isotherms, the heats of immersion in these liquids,
and the basal spacing, i.e. the expansion of the interlayer space.
Both hydrophobic layered double hydroxides (LDHs) adsorbed n-hep-tane, benzene, toluene, and n-pro-panol between the layers with considerable increase of the basal spacing. Interlamellar swelling of the hydrophobizised
LDHs in n-heptane was fundamentally different to the behavior of hydrophobized 2 : 1 clay minerals (smectites, vermiculites). The surface
excess isotherms for benzene/ heptane mixtures were U-shaped and indicate preferential adsorption of benzene. Dodecylbenzene
sulfonate double hydroxide preferentially adsorbed propanol from n-propanol/ toluene mixtures but the dodecyl-sulfate derivative adsorbed both compounds.
Received: 23 January 1997 Accepted: 10 February 1997 相似文献
6.
J. Rychlicka-Rybska 《Colloid and polymer science》1998,276(12):1140-1144
The influence of temperature on the composition of mixed monolayer formed at the methyl alcohol/acetic acid aqueous solution
was examined by surface tension measurements. Surface tension of various two-component solutions was obtained at 10, 20 and
28 °C temperatures in the 0–0.5 M range of bulk concentration of alcohol and acid, respectively. Three independent methods,
i.e., the Gibbs adsorption equation (GAE), regular solution approximation (RSA) and Butler adsorption isotherm (BAI) were
applied to calculate surface composition of the methyl alcohol/ acetic acid mixed monolayer. It was shown that in the temperature
range of 10–28 °C the surface molar fraction of the solutes remained constant for the fixed bulk concentration of alcohol
and acid. Additionally, based on the RSA and BAI methods, we showed there were no interactions between solute molecules in
the mixed monolayer in the studied range of concentrations.
Received: 18 December 1997 Accepted: 8 May 1998 相似文献
7.
Amphiphilic diblock copolymers consisting of a hydrophobic polystyrene block (PS) and a hydrophilic poly(ethylene oxide)
block (PEO) with block sizes of 1000 or 3000 g/mol for both blocks were studied at the air/water and toluene/water interface.
Measurements of the film pressure π of spread monolayers at the water surface reveal two limiting regimes of the π−a
m isotherms, in which the mean molecular area a
m is determined either by the size of the hydrophilic or the hydrophobic blocks of the PS-PEO molecules. The interfacial activity
of the block copolymers at the toluene/water interface was studied by measuring the interfacial tension σ over a wide range
of concentrations. Pronounced differences in the temperature dependence of the interfacial tension were observed, depending
mostly on the block length of the hydrophilic PEO block. From the temperature dependence of σ it is inferred that for the
block copolymers with the PEO block size of 3000 g/mol the phase inversion temperature (PIT) is well above 60 °C while for
those with a PEO block size of 1000 g/mol the PIT is below or near 25 °C in the toluene/water system.
Received: 5 February 1998 Accepted: 16 February 1998 相似文献
8.
A. N. Araújo José A. M. Catita José L. F. C. Lima Elias A. G. Zagatto 《Fresenius' Journal of Analytical Chemistry》1998,360(1):100-103
A monosegmented flow system (MCFA) is proposed to achieve slow enzymatic spectrophotometric determinations, here applied
to the determination of triglycerides in blood serum. The sample (4.5 μL), enzymatic reagent (150 μL) and an air plug (100 μL)
are simultaneously inserted into a carrier stream buffered to pH 7.9 (Tris ⋅ HCl). In order to avoid the cumbersome step of
air removal, a relocating detector was used. This system handles about 60 samples/h, yielding precise results (r.s.d. usually<2.5%).
Sensitivity is 56 mAU ⋅ L/mmol up to 6 mmol/L triglycerides. Accuracy was assessed by running 50 samples already analysed
by a conventional procedure yielding the equation CMCFA(mmol/L)=1.00(±0.04) CRef(mmol/L)−0.03(±0.08); r=0.990.
Received: 22 January 1997/Revised: 12 March 1997/Accepted: 28 March 1997 相似文献
9.
The binding behavior of dodecylpyridinium chloride to sodium polyphosphate of various degrees of polymerization (DP) was
studied by means of a potentiometric titration method using a surfactant-selective electrode in the presence of 10 mM NaCl
at 30 °C. Binding isotherms were analyzed by direct calculation of a matrix expressing the partition function. It is found
that binding affinity depends prominently on the polymer chainlength when the DP value is less than ca. 35, but becomes nearly
independent on DP thereafter. No binding was observed for linear triphosphate or cyclic trimetaphosphate anions. The picture
that arises for the binding is that the polymer’s end-effect reduces the apparent cooperativity, while the hydrophobic interaction
with neighboring surfactant remains constant because of the short-range nature of the interaction. The so-called end-effect
is associated with a superimposition of electrostatic potentials around the polymer rods. Both the matrix method and the Satake–Yang
equation were carried out for simulations, and the matrix one shows a better fitting with the experimental data for the short-chain
polyelectrolyte.
Received: 1 July 1997 Accepted: 21 August 1997 相似文献
10.
Temperature-sensitive micron-sized monodispersed composite polymer particles were prepared by seeded copolymerization of
dimethylaminoethyl methacrylate and ethylene glycol dimethacrylate with 1.77 μm-sized monodispersed polystyrene seed particles.
The change in surface property at temperature above and below 35 °C was examined by differential scanning calorimetry, trypsin
activity and the adsorption/ desorption behaviors of low molecular weight cationic emulsifier as well as biomolecules.
Received: 6 August 1997 Accepted: 16 January 1998 相似文献
11.
Christopher J. G. Plummer Rudolf Gensler Hans-Henning Kausch 《Colloid and polymer science》1997,275(11):1068-1077
Melt crystallized isotactic polypropylene thin films of thickness between 30 and 100 nm have been investigated by high-resolution
transmission electron microscopy at room temperature. The c-axis projection of the 2*31 helices and their packing in the lattice were clearly visible in flat-on lamellae of the α-phase following reconstruction
from the components of the image Fourier transform corresponding to the (1 1 0) and (0 4 0) lattice planes, and the image
power spectra also indicated contributions from (1 3 0) and (0 6 0) relfections, corresponding to a line resolution of about
0.35 nm. These results are discussed in terms of Bloch wave calculations based on the generally accepted structure for the
α-phase. Attempts to obtain lattice images of the β-phase in isotactic polypropylene and melt crystallized syndiotactic polypropylene
under similar operating conditions are also briefly discussed, although these provided relatively little structural information.
Received: 27 June 1997 Accepted: 15 August 1997 相似文献
12.
D. Y. Kwok A. Leung A. Li C. N. C. Lam R. Wu A. W. Neumann 《Colloid and polymer science》1998,276(6):459-469
Low-rate dynamic contact angles of 22 liquids on a poly(n-butyl methacrylate) (PnBMA) polymer are measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It is found that 16 liquids yielded
non-constant contact angles, and/or dissolved the polymer on contact. From the experimental contact angles of the remaining
6 liquids, it is found that the liquid–vapor surface tension times cosine of the contact angle changes smoothly with the liquid–vapor
surface tension, i.e. γlv cos θ depends only on γlv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert
and non-inert (polar and non-polar) surfaces [34–37, 45–47]. The solid–vapor surface tension calculated from the equation-of-state
approach for solid-liquid interfacial tensions [14] is found to be 28.8 mJ/m2, with a 95% confidence limit of ±0.5 mJ/m2, from the experimental contact angles of the 6 liquids.
Received: 12 September 1997 Accepted: 22 January 1998 相似文献
13.
I. Shimizu H. Okabayashi N. Hattori K. Taga A. Yoshino C. J. O’Connor 《Colloid and polymer science》1997,275(3):293-297
Changes in the 13C and 1H NMR chemical shifts of the silane coupling agent (3-aminopropyltri-ethoxysilane, APTS) in toluene, which were detected as
the concentration of APTS increased, have been interpreted in terms of the formation of micelles and the presence of a critical
micelle concentration (CMC) equal to ca. 0.47 mol 1-1. For the protons of the n-propyl segment, 1H NMR splitting patterns have been analyzed and conformations of the propyl segment have been discussed. Plots of relative
absorbance of the two NH2 stretch IR bands at 3324 and 3384 cm-1 against concentration provided an inflection point (corresponding to the CMC) at a value equal to 0.46 mol 1-1. Thus, consideration of the interaction of APTS with a surface must take into account the presence of both APTS aggregates
as well as APTS monomers.
Received: 16 August 1996 Accepted: 26 September 1996 相似文献
14.
The hydrolysis of SbCl3 in hydrochloric acid solution (2.0 mol dm-3 HCl) at 0 °C yields an amor-phous product consisting of uniform spherical particles (d∼0.5 μm), which on continuous aging at the same temperature transform to larger crystals, indicated by XRD to be Sb4O5Cl2. In contrast, in the same solution kept at 25 °C crystalline particles of the same composition form directly after an induction
period and then grow with time. The final products, obtained at 0 °C and 25 °C consist of aggregated subunits. These powders
on calcination in nitrogen are converted to Sb2O3 and in air to Sb2O4.
Received: 23 June 1997 Accepted: 1 July 1997 相似文献
15.
C. Vanderdonckt M. Krumova F. J. Baltá Calleja H. G. Zachmann S. Fakirov 《Colloid and polymer science》1998,276(2):138-143
Poly(ethylene terephthalate) (PET) was annealed in vacuum at different temperatures (190–260 °C) for different times (10 min–24 h)
in order to examine the mechanical properties (microhardness) of PET samples with a wide range of molecular weights (10 000–120 000).
Short annealing times result in a twofold decrease in mol. wt. due to hydrolytic decomposition. However, long annealing times
give rise to a substantial molecular weight increase. It is found that microhardness (H) rises linearly with the degree of crystallinity obtained during up-grading of mol. wt. and its extrapolation leads to H-values of completely crystalline PET, H
PET
c=405 MPa for samples with conventional mol. wt. and of 426 MPa for samples with mol. wt. higher than 30 000. It is shown that
the increase of mol. wt. for each set of samples with a given range of degree of crystallinity also causes a slight increase
of H. The influence of mol. wt. upon hardness is discussed in the light of the changes in the physical structure (crystallinity,
crystal thickness) which is formed at given heat treatment conditions.
Received: 29 April 1997 Accepted: 23 September 1997 相似文献
16.
The association behaviour of triblock copoly(ethylene oxide/tetrahydrofuran/ethylene oxide), in particular E100T27E100, in aqueous solutions has been investigated by means of static and dynamic light scattering, nuclear magnetic reso-nance
(NMR) and surface tension techniques. On raising the polymer concentration at room temperature, the copolymer aggregates to
form micelles with an aggregation number of about 105 (R
G, mic≈15 nm and R
H, mic≈13 nm, as revealed by light scattering and FT-PGSE NMR measurements, respectively). The micelles are kinetically quite stable,
the micellar lifetime is shown to be more than 1 h. The residence time of a single unimer in a micelle is more than 140 ms.
The apparent radius of gyration R
G, mic is fairly independent of concentration, but large effects are observed on varying the temperature. Raising the temperature
initially results in an increase of the apparent micellar size, followed by a maximum at an intermediate temperature (≈45 °C).
At higher temperatures a contraction of the micelles is observed. The shape of the micelles also appear to vary in this temperature
interval. The interactions responsible for these phenomena are discussed in terms of, e.g., the temperature-dependent solubility
of the alkylene oxide segments in water and polydispersity effects.
Received: 29 January 1996 acccepted : 4 November 1996 相似文献
17.
G. W. Chądzyński P. Staszczuk D. Sternik M. Błachnio 《Journal of Thermal Analysis and Calorimetry》2008,94(3):623-626
Properties relating to porosity of solids (fractal dimensions, surface roughness parameters) were evaluated from atomic force
microscopy (AFM) and nitrogen adsorption-desorption isotherms measured at 77 K for selected high-temperature [(RE) Ba2Cu3O7−x, RE=Y, Sm] superconductors. Adsorption capacity, specific surface area, fractal dimensions were determined from adsorption-desorption
isotherms. The adsorption isotherms of all samples were S-shaped and belong to type II according to the IUPAC classification.
A linear relationship was demonstrated between the fractal coefficients calculated by using the two methods and values of
adsorption capacity of monolayer. 相似文献
18.
Yan Bai Gui-Ying Xu Hong-Yuan Sun Xiao-Deng Yang Ai-You Hao Jin-Yu Pang Hou-Jian Gong Ming-Qi Ao 《Colloid and polymer science》2010,288(4):415-421
The surface property of an amphiphilic cyclodextrin 2-O-(hydroxypropyl-N,N-dimethyl-N-dodecylammonio)-β-cyclodextrin (HPDMA-C12-CD) was investigated using oscillating bubble rheometer and electrical conductivity method at different temperatures. The
surface tension and dilational viscoelasticity of HPDMA-C12-CD were provided. The results showed that HPDMA-C12-CD could adsorb on the air–water interface, which decreased the surface tension of water efficiently. Critical micelle concentration
(cmc) can be clearly defined from the surface tension isotherm. pC20 and π
cmc were derived from the surface tension isotherms as well. The thermodynamic parameters (ΔG
0
m , ΔH
0
m , −TΔS
0
m) derived from electrical conductivity indicated that the micellization of HPDMA-C12-CD was entropy-driven at lower temperature, while it was enthalpy-driven at higher temperature. The dilational modulus appeared
a maximum value while the phase angle appeared two maxima as a function of HPDMA-C12-CD concentration. 相似文献
19.
The water desorption isotherms are determined in three cellulose acetate membranes with different acetyl content as a function
of p/p
0 at 10–40 °C. The partition coefficients (adsorbed water over water pressure) show a minimum at p/p
0=0.5–0.6. This indicates a two energy mechanism. The agreement of our results with the BET adsorption isotherms only till
p/p
0<0.3 shows that a two energy adsorption mechanism is valid only for small water contents, probably one hydrate layer and a
second more liquid-like water layer. At large p/p
0, the adsorbed water becomes more and more liquid like by polarization of the hydrogen bonds. The heat of desorption is larger
than the vaporization heat of water ΔH
vap(H2O). It decreases with increasing water content asymptotically to ΔH
vap(H2O). The cause may be a larger van der Waals interaction of the hydrate layer due to coordination numbers larger than 4.4 as
in liquid water. Additionally, we found a hole adsorption process by sorbing unpolar solvents. The water and methonal adsorption
are 100 times larger due to a swelling mechanism depending on the number of acetyl groups in the membranes. The amounts of
n-alcohols sorbed decrease with their chain length.
Received: 25 April 1997 Accepted: 10 June 1997 相似文献
20.
The analysis of the interaction of micelles formed by a blockcopolymer is given by means of small-angle X-ray (SAXS) and
small-angle neutron scattering (SANS). The blockcopolymer consists of poly(styrene) and poly(ethylene oxide) (molecular weight
of each block: 1000 g/mol) and forms well-defined micelles (weight-association number: 400, weight-average diameter: 15.4 nm)
in water. The internal structure has been studied previously (Macromolecules 29:4006 (1996)) by SAXS. There it has been shown
that the micelles are spherical objects. The structure factor S(q) as a function of the scattering vector q (q=(4π/λ) sin (θ/2); λ: wavelength of the radiation in the medium; θ: scattering angle) can be extracted from both sets of small-angle
scattering data (SANS: q≤0.4 nm-1; SAXS: q≤0.6 nm-1). It is shown that particle interaction in the present system can be described by assuming soft interaction which is modeled
by a square-step potential.
Received: 12 May 1997 Accepted: 9 July 1997 相似文献