Determination of dispersive and nondispersive components of the surface free energy of glass fibers

The dispersive component _s ^d of the surface free energy of glass fibers and its interaction energy with alkanes, benzene, 1-nitropropane, ethyleneglycol, glycerol, formamide, and water were quantitatively determined by the tensiometric method within two liquids. The values of nondispersive interaction energy I _SL ^p were found to be a linear function of the square root of the nondispersive component of the surface free energy of liquids. This suggests that the nondispersive interaction energy may be represented by the geometric mean of the nondispersive component of the surface free energy of a solid and a liquid. The slope gave the nondispersive component _s ^p of the surface free energy. The _s ^p values are 33 and 14 mJ/m² for the untreated and aminosilane-treated fibers, respectively, suggesting that organophilic character has developed on the surface after aminosilane treatment. The _s ^p value was almost similar after the treatment, probably because of the polar characteristics of amino groups.     

Microhardness and surface free energy in linear polyethylene: The role of entanglements

The microhardness of a series of melt crystallized samples of linear polyehtylene was investigated in a wide range of molecular weights. The x-ray long period was analyzed to study the variation of the hardness-derived constantb as a function of molecular weight (M ). It is pointed out thatb offers a measure of the hardness depression due to the finite thickness of the lamellar crystals. The data obtained show that the increase and final leveling-off (forM 200 000) ofb withM parallels the concurrent increase of the surface free energy, as derived from DSC experiments. Results are discussed using the concept og chain folded lamellae as thermodynamically stable non-homogeneous microphases. Comparison of experimental and calculated data supports the view that the number of molecular entanglements, segregated onto the defective surface boundary of the heterogeneous crystals influence the shearing mechanism within the mesocrystals and thereby control the yield behavior of the material.     

Contact angle hysteresis in carbon fibers studied by wetting force measurements

The surface free energy of polyacrylonitrile carbon fibers was investigated by using the Wilhelmy technique. The difference in surface free energy between immersion and emersion was observed for the carbon fiber pyrolyzed at 2500 °C.In contrast, the hysteresis disappeared with repyrolyzation of the carbon fibers at 3000 °C. Auger electron spectroscopic analysis indicated that the surface of the latter carbon fiber (repyrolyzed at 3000 °C) consisted of the basal planes of graphite. Rough surface topography of the carbon fiber repyrolyzed at 3000 °C, as observed by scanning electron microscope, did not affect the hysteresis. Therefore, the contact angle hysteresis was attributed to the chemical adsorbants on the activation sites of the fiber surfaces, as detected by Auger electron spectroscopy.     

Estimation of surface free energies and hamaker constants for fibrous solids by wetting force measurements

Wetting force at three-phase line was measured by the Wilhelmy technique using fibrous solids/liquid/liquid systems. Advancing and receding contact angles were calculated from the wetting forces during fiber immersion and emersion. The obtained results showed that contact angle hysteresis was due to the heterogeneity of the fiber surfaces. The dispersive and polar components of surface free energies of the fibers were determined from the advancing and receding contact angles, respectively. The Hamaker constants of the fibers were estimated from the dispersive components of their surface free energies.     

Surface characterization of modified glass fibers by inverse gas chromatography

The dispersive component of the surface free energy _d ^s of glass fibers and their acid-base interaction can be evaluated by the measurement of specific retention volumes of several kinds of probe molecules by use of an inverse gas chromatography. The effect of the treatment of glass fibers with silane-coupling agents was also evaluated. The specific retention volumes of n-alkanes changed linearly with theirC number or vapor pressure. Those of polar molecules varied with their donor number (DN) or acceptor number (AN). The _s ^d values and electron-accepting or donating abilities depended upon the kind of functional groups contained in the coupling agents.     

Molecular properties of acetone and some of its chloroderivatives adsorbed at the surface of water

The relations between the electric surface potential (V) and the surface tension () of aqueous solutions of acetone, chloroacetone, 1,3-dichloroacetone, and their concentration were investigated. The vertical components of dipole moments of the above mentioned compounds were determined using the Helmholtz equation. The calculations were carried out on the basis of surface excess values, which were obtained from surface tension measurements and surface potential changes. Once the vertical component of dipole moments were found and the orientation of adsorbed molecules was assumed, the local dielectric permittivities of the surface monolayer were estimated.     

Hard elastic polypropylene-nature,internal friction,and surface energy

Tensile tests were performed at low temperatures, both in liquid and gaseous nitrogen and also at room temperature, using a series of polypropylene (PP) samples with various technological parameters. Crystalline morphology was also measured for film samples. The results show that liquid nitrogen or solvents can induce materials to create hard elasticity, which strongly supports the bulk-microfibril composite structure proposed by Baer et al., and suggests that the nature of hard elasticity is essentially a craze phenomenon. Three conditions of forming hard elastic structure are discussed. The results from long-time relaxation of hard elastic polypropylene (HEPP) and the improvement of necking of the PP samples in ethanol and water suggest that elastic recovery is reduced by internal friction. The relation between morphology and elasticity is also discussed. The methods of estimating the contribution of surface energy in the recovery process and the increase of surface energy of HEPP during the stretching process are provided. The contribution of surface energy to recovery is about 43% to 66% in the first cycle and after relaxation for 1 h at a maximum of 50% strain. The increased surface energy during stretching is about twice the recovery work done by surface energy.     

Characterization of wood fibers modified by phenol-formaldehyde

Wood-fiber phenol-formaldehyde-resin (PFR) modified surfaces, obtained from the adsorption of a PFR/water solution, are investigated as a function of the nature and the amount of PFR adsorbed. Surface are measurements are performed by using krypton adsorption at 77 K. Chemical modification is monitored by the electron spectroscopy for chemical analysis (ESCA) technique and the surface energy by the inverse phase gas chromatography (IPGC) method at infinite dilution. The London dispersive componentγ _S ^L of the surface energy shows a relationship to the concentration of carbon and oxgen at the fiber surface.γ _S ^L increases from 27.5 mN·m⁻¹ for the untreated fiber to 42.5 mN·m⁻¹ for the fibers treated with 20% high molecular-weight-grade phenol-formaldehyde. The surface atomic ratio O/C determined using the ESCA technique exhibits a decrease from 44% for untreated to 31% for treated samples. Surface area also decreases from 2.09 m²/g to 1.50 m²/g. The PFR adsorbed by wood fibers is observed as the dispersive component of surface energy starts to increase, as the surface oxygen concentration decreases, and on the surface area of the wood fiber.     

The adsorption process of some acetic acid derivatives at the water/air interface

The adsorption of trifluoro-, trichloro-, tribromo-, and trimethylacetic acid at the water/air interface is discussed on the basis of surface tension measurements. The process of adsorption is described by Henry's and Langmuir's isotherm equations. The obtained results allow calculation of the standard free energy of adsorption of investigated molecules and the contribution to this energy of hydrophobic groups of these molecules.     

Stability of spherical and rod-like micelles of ionic surfactants,in relation to their counterion binding and modes of hydration

Aqueous salt solutions of ionic surfactants in both spherical and rod-like micelles have been treated on the basis of a statistical thermodynamic theory, and the double logarithmic relationship between micelle molecular weight and ionic strength is derived for each micelle. Counterion binding on both micelles are assumed to occur specifically, and their degrees of dissociation are related to the slopes of the linear double logarithmic relations. It is found from the relationship observed for typical surfactants that the effective charge of spherical micelles is 29±4. The degree of dissociation of rod-like micelles of these surfactants is primarily determined by the counterion species, yielding values 0.8 for Na⁺, 0.4–0.6 for Cl^– and 0.2–0.3 for Br^–. Hydrophilic hydration of both micelles can be evaluated from the intercepts of the linear relations. Hydrophilic hydration acts repulsively in spherical micelles, while it is attractive or much less repulsive in rod-like micelles.     

Stability of modified surface CaCO3 in the non-polar medium

The adsorption isotherm of methacrylic acid (MAA) and polymethacrylic acid (PMAA) molecules on CaCO₃ were studied. The isotherm of (MAA) adsorption from cyclohexane was found formed from two steps, while that of (PMAA) from ethanol is formed from one step. The effects of surface modification of CaO₃ with (MAA) and (PMAA) in the sedimentation properties in a non-polar medium (cyclohexane) have been studied. It was found that the most stable suspension formed is concerned with monolayer surface coverage for the two adsorptives. Also, studies were made for the rheological properties of concentrated suspension of CaCO₃ modified with (MAA) and (PMAA) in a paraffin oil. The equilibrium flow curves of CaCO₃ modified with (PMAA) suspensions exhibit pseudoplastic characteristics, accompanied by some degree of complex thixotropy, while that modified with (MAA) exerts a thickening effect with rheopexy characteristics.     

Preparation of muscovite with ultrahigh specific surface area by chemical cleavage

The specific surface area of a muscovite sample increases drastically after exposure to a LiNO₃ solution, e.g., from 3.4 m²/g, corresponding to platelets of ca. 200 silicate layers, to 295 m²/g (platelets of ca. 2–3 silicate layers) after treatment at 180°C under atmospheric pressure for 46 h. The efficiency of the cleavage process decreases with decreasing temperature (down to 50°C). The LiNO₃/H₂O weight ratio is also very important: at 130°C and a reaction time of 46 h, for instance, a value in the range of 1.7–1.8 leads to the highest specific surfaces. The cleaved products have the form of strong papers that disperse readily in water. During the cleaving procedure, not only the particle thickness, but also the diameter decreases. There is no evidence of damage or partial dissolution of the silicate structure after cleavage, by IR spectroscopy and yield. The use of LiCl also leads to an increase in specific surface area, but the effect is weaker than in the case of LiNO₃. Treatment with some other alkaline and alkaline earth nitrates and chlorides did not increase the specific surface area of muscovite significantly.     

Characteristic changes of pH during the alkalization of latex dispersions of the ethyl acrylate — methacrylic acid copolymers

The titration curves of latex dispersions of ethyl acrylate — methacrylic acid copolymers have a rather complex shape which indicates a strong dependence of the apparent dissociation constant of carboxylic groups on the degree of neutralization and copolymer composition. These dependences seem to be related to changes in the macroscopic structure (swelling and disintegration) of dispersion particles during alkalization.     

On the collision efficiency approach to flocculation

The collision efficiency approach to flocculation is analyzed on the basis of a model describing the probability of aggregation by polymer bridging. The model allows for the effect of the randomness of distribution of polymer over particles as well as the effect of simultaneous coagulation and weak flocculation. It is argued that the collision efficiency approach is applicable to a rather limited range of experimental systems and provides a qualitative understanding rather than a quantitative theory of the relationship between flocculation and adsorption.     

Miscibility of dodecyltrimethylammonium bromide and dodecyltrimethylammonium chloride in surface-adsorbed film and micelle

Surface tension of aqueous solutions of mixtures of dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium chloride (DTAC) has been measured and analyzed by using thermodynamic relations. The adsorbed film has been found to contain more DTAB molecules than the solution. The shape formed by the curves of the total molality at constant surface tension against the solution and surface compositions indicates the ideal mixing of the DTAB and DTAC molecules in the adsorbed film. Micellar composition has been estimated at the critical micelle concentration (CMC). The micelles have been found to be richer in DTAB than the solution, but poorer in DTAB than the adsorbed film at the CMC. The DTAB and DTAC molecules have been shown to mix ideally in the micelles. From the comparison with the results on the system of decylammonium bromide and decylammonium chloride, it has been concluded that, on the mixing of surfactants differing only in counter ions, the adsorbed film is influenced more significantly by the ionic head group of the surfactant than the micelle.     

Strength of fibers from wholly aromatic polyesters

A theory of the strength (or the tenacity) of highly oriented Liquid Crystal Polymer (LCP) fibers was developed, and its results were compared with existing tensile strength data of fibers of a copolymer of 1,4-oxybenzoate and 6,2-oxynaphthoate. A basic premise of the theory is that the mechanical load transfer between polymer chains is through intermolecular interaction which acts in a manner similar to that of shear stress, and that the fiber strength is primarily governed by the intermolecular adhesion strength. The theory also incorporates the effects of MW, MW distribution, and the chain orientation distribution. Analysis of the experimental tenacity data demonstrates that the present theory can quantitatively describe the variation of the tenacity of LCP fibers with MW both in the as-spun and in the heat-treated states. The theory further predicts that the predominant factor governing the tenacity of LCP fibers is primarily due to MW increase due to solid-state polymerization. It is also demonstrated that the intermolecular adhesion between LCP chains is relatively weak and does not improve with heat treatment. The absence of factors that limit the MW increase (i.e, imbalanced end-groups and side reactions of end groups) is a prerequisite for fast heat treatment of a LCP fiber to a high tenacity.Symbols A _f the cross-sectional area of a single polymer chain - E _f the theoretical modulus of a polymer chain - G _m the shear modulus of fiber - h(l) the chain length distribution function - l the chain length - l the number average chain length - l _c the length of chain units that are bonded to adjacent polymer chains - n ² 4G _m/CE_f - N _c the number of polymer chains per unit area perpendicular to the fiber axis - P _b the probability that a chain does not have a chain end in the fracture zone - P _e the probability that a chain has, at least, a chain end in the fracture zone - q _e,q _b the probability of finding an ending and a bridging polymer chain, respectively, in the fracture zone - l the length of fracture zone - the elongation of a polymer chain - the chain orientation angle - _f the normal stress that acts on a polymer chain - _fu the fiber tenacity - _e the shear stress that acts on a polymer chain surface Dedicated to Prof. Dr. rer. nat. Wolfgang Hilger, Chairman of Hoechst A.G. in honor of his 60th birthday     

Changes in electrokinetic properties of natural rubber latex after surface chemical modifications

High-ammonia latex concentrate prepared from doubly-concentrifuged fieldHevea latex was exhaustively dialyzed to remove any residual water-soluble non-rubber constituents. The specially purified latex was then treated with specific chemical reagents to modify the surface ionogenic groupings originally present on the latex particle surface. The electrophoretic mobility of the modified latexes was investigated as a function of pH. The change in electrokinetic properties of the surface-modified latex was explained in terms of chemical modification to the ionogenic groups of the adsorbed layer of proteins and long chain fatty acid soaps on the latex particle surface, the negative charges of which are primarily responsible for the colloidal stability of the latex. For comparison direct extraction of the long-chain fatty acid soaps from the specially purified latex by solvent was also carried out. Present results indicate that the number of carboxyl groups from the adsorbed long-chain fatty acid soaps plays a major role in the stabilization of the latex concentrate. In comparison the contribution of negative charges from the adsorbed proteins towards the stability of the latex is of less importance.     

Heat of micelle formation: Effect of counterions with concentrated,diffused, and separated electric charges

Heats of micelle formation were estimated from calorimetric measurements of anionic surfactants to see if there is any effect of the electrical charge of the counterion on micelle formation from the viewpoint of enthalpy change. The cationic counterions used are Na⁺ and Cu²⁺ for the concentrated electric charge, MV²⁺ for the diffused and 1,1-(1,)-alkanediyl)bispyridiniumions n=2, 4, 6, 8, 10, 12, 14 for the separated. The heat of micelle formation was obtained by subtracting an enthalpy change of dissolution of surfactant solid precipitated below the micelle temperature range (MTR or Krafft point) from a heat of complete dissolution of the precipitated surfactant solid around the MTR. The heats thus evaluated were found to be much more temperature-dependent than counterion-dependent. They were compared with the enthalpy change calculated from the CMC change with temperature, and the big difference between them was discussed from a thermodynamic point of view.     

Force-length relation for a short freely jointed chain: mass and volume dependence

We evaluate the force-length relation for short model chains. It is shown that this relation is markedly different when evaluated for static and dynamic model chains with rigid segments. The relation also differs for chains with rigid segments when they are isolated and coupled to a canonical heatbath, respectively. Furthermore, it is derived that the variation of the masses along the chain only has a small influence on the force-length relation. On the other hand, restricting the motion of the chain by walls perpendicular to the chain extension has a pronounced effect. We especially find that in this situation the chain has a finite equilibrium length.Dedicated to Professor W. Pechhold on the occasion of his 60th birthday