Further electron microscope observations on polyethylene I. Granule structure of the melt as an artifact

There are still two opinions on the fine structure of polymer melts and glasses: (a) that the structure is similarly homogeneous to that in lower molecular weight materials and (b) that the structure shows larger short-range order regions (2–20 nm), which consist of bundeled segments of the chain molecules. Whereas opinion a relies more on indirect methods of investigation, opinion b is based mainly on fine granular structures which become visible in electron microscope investigations of surfaces of glassy solidified polymers. Such a fine structure can now be observed directly in a polyethylene melt. However, the structure is exposed as an artifact, so opinion a is supported.Dedicated to Prof. Dr. R. Bonart. Presented at the colloquium on 18.1.1985 in Regensburg on the occasion of his 60th birthday.Presented at the 32nd Meeting of the Colloid Society and Berlin Polymer Conference 1985, 2.–4.10.1985 in Berlin.     

Structure transfer from a polymeric melt to the solid state. Part II: Dependence on molecular weight

Melt spinning experiments of polyethylene, using a high quenching rate have been carried out. Molecular weight has been varied. From measurements of the mechanical properties of the monofilaments produced it is concluded that melt history influences the solid state behavior. This is reflected in the hypothesis of a transference of knots, preexisting in the melt into the solid state. Measurements of the elastic recovery allow to offer an interpretation, in which this network of knots does not percolate, until a critical value of the molecular weightM _{c knot}10⁵ is surpassed. The possible influence of these knots on the mobile entanglements is discussed.On leave from the Institut für Technische und Makromolekulare Chemie, Universität Hamburg, Hamburg, Germany.     

Melt drawing as a route to high performance polyethylene

Well established routes for obtaining stiff and strong polyethylene (PE) involve solid state drawing either of solution crystallized gel films or melt crystallized spherulitic PE. The aim of this work is to show the potential of melt deformation as an alternative route for obtaining highly oriented products. Our previous work on the melt deformation route showed that oriented PE fibers could be directly extruded under appropriately controlled conditions [8,9]. Here, we show that PE films (or filaments) can also be melt drawn in the temperature window 130–160 °C, thus yielding oriented products. The advantage of melt drawing over direct melt extrusion is that it allows a wider operational latitude and thus does not require such carefully controlled conditions.The morphology produced by melt deformation is different from solid state deformation and consists of extended chain fibrils with platelet overgrowths. The relative amount of fibrils and platelets depends on operating parameters. The temperature window of PE melt drawing is identified with the regime where some flow induced crystallization takes place. The conditions for melt drawability are of wider generality for crystallizable flexible chain polymers. They are: (i) adequate strain rate to overcome entropie resistance to chain extension, (ii) but not high enough to activate the elastic response of the transient networks in the entangled system, (iii) sufficient strain to fully extend the chain, (iv) appropriate temperature for flow-induced crystallization and strain hardening, and (v) cooling to freeze the oriented structure.Ultra high molecular weight PEs were not the most suitable for melt drawing due to their high recoverable elongation in the melt (melt elasticity) in addition to added limitations imposed by their nascent grain systeme. Our work suggests that an optimum molecular weight for melt drawing is¯M _w(400–900)×10³ with further possibilities for improvement through multimodal distributions.     

XPS analysis (ESCA) of the surface composition of poly(styrene/2-hydroxyethyl methacrylate) microspheres produced by emulsifier-free emulsion polymerization

Polymer microspheres composed of various compositions of styrene and 2-hydroxyethyl methacrylate (HEMA) were produced by batch emulsifier-free emulsion polymerization. The HEMA content at the surface, [HEMA] _s , of the microspheres powdered by freeze-drying was determined by both quantitativeC ^1s /O ^1s analysis andC ^1s peak shape analysis of the x-ray photoelectron spectroscopic spectra. When the HEMA content in the microsphere, [HEMA] _p , was less than about 5 mole%, the [HEMA] _s values determined by the two different methods showed good agreement. At [HEMA]_p above 5 mole %, [HEMA]_s values determined by the first method were about 15 mole % greater than those determined by the second. They both showed a similar tendency with the [HEMA] _s being higher than the [HEMA] _p , e.g., when [HEMA] _p was 1 mole %, [HEMA] _s was 11 mole %. The intensity of the satellite peak due to the ^* transition of the benzene ring of the styrene component decreased with an increase in [HEMA] _p , to zero at 5 mole % of [HEMA] _p . These results indicate that the HEMA component is localized at the surface.Part CVIII of the series Studies on Suspension and Emulsion.     

X-ray scattering study of molecular order in a liquid crystal-side group polysiloxane

The molecular structure of a polysiloxane with phenyl benzoate mesogenic side groups was investigated in an x-ray scattering study in the partially crystalline, smectic and nematic phase, and in the melt. In the crystalline phase polymer molecules have the form of straight ribbons with a double-comb-conformation. A bilayer structure is built up by regular stacking. Layers are the dominating structure element not only in the crystalline and smectic phase, but also in the nematic phase, and even in the isotropic melt. Layers are planar in the smectic phase and curved in the nematic phase, with an asymmetric distribution of the normal vectors about the director. In the isotropic melt there is evidence for the occurrence of clusters with layer-like short-range order.     

Mechanism of the grafting of organosilanes on mineral surfaces. IV. Phenylderivatives of sepiolite and poly (organosiloxanes)

Grafting reactions of phenyl groups on silica substrates using as reagents various phenylsilanes with variable distances between the silicon atoms and the aromatic ring by 0, 1, and 2 methylene groups [Si–(CH₂) _n –C₆H₅] were studied. Two different silicates have been selected as source of silica: sepiolite and tetraethyl-orthosilicate (TEOS). Sulfonic- and nitro-derivatives prepared from these phenyl compounds by electrophilic substitution reactions, have been obtained. The mechanism of these processes has been studied in relation to the number of methylene separating groups belonging to the starting reagents. The characterization of such systems has been achieved by XRD,²⁹Si and¹³C NMR/MAS, IR, and laser microprobe mass spectrometry.Parts I, II and III published in this Journal (1978) 256:135–139, (1979) 257:178–181 and (1985) 263:1025–1030     

The orientational state of uniaxially stretched PMMA

Uniaxially stretched samples of PMMA were investigated by Brillouin Spectroscopy (BS). From the velocity of hypersound we could determine most of the elastic constants. Using a recently developed analysis [1] it is demonstrated that the properties of this polymer can be well described by the aggregate model. This result offers the possibility of mapping the mechanical properties by birefringence measurements. The dependence of the fourth momentP ₄ on the second momentP ₂ is identical with that determined for PC [2] and follows, in the measured range, that of an affine orientational state. Nevertheless, the dependence on the stretching ratio differs for different molecular weights. Thus the partition of the deformation into an orientational and an elongational contribution, as has been proposed [3], seems to be well founded.The partition depends on the stretching conditions.     

Donator acceptor behavior of aerosil in several organic liquids

Aerosil is studied with regards to its acceptor behavior by means of electrokinetic measurements and UV measurements in various organic liquids. Whereas the values of the general negativ zeta-potential only approximately correspond with the donor number of the liquids determined according to Gutmann, Marie and Gal, and Kravtzov et al., an excellent agreement between zeta-potential and the UV maximum of a dicyano-bis(1,10-phenanthrolin)-ferric [Fe(phen)₂(CN)₂] complex adsorbed at the solid-liquid interface was found. The fact that traces of water decrease the negative zeta-potential of aearosil in organic liquids is attributed to hydration of the aerosil surface.Dedicated to Professor Dr. Josef Schurz on the occasion of his 65th birthday.     

New conducting polymers, 3. Doping,stability, electrical,and optical characteristics of poly-(P-phenylphosphoethynediyl)

Studies on direct-current electrical conductivity and optical properties of a new solution of processable conducting polymer are reported. Electrical conductivity of thin films of the polymer on glass plate at room temperature was 6×10⁻⁶ S/cm. Study of conductivity with variation of temperature does not provide any definite thermal activation energy, which is in accordance with the amorphous nature of polymer. Optical absorption data adopting the Bardeen equation showed that maximum ‘optical gap’ (E _g ) is 3.30 eV. Doping with Br₂-vapor was found to be only partially effective in decreasingE _g by 0.43 eV. The polymer was found to be quite stable under normal atmospheric conditions. Environmental stability of both undoped and doped polymer has been discussed. Part 2: [5]     

Stability of chromium dioxide particles in aqueous media

An investigation was carried out to characterize the dissolution behavior of stabilized and unstabilized CrO₂ particles in water, used in magnetic recording. Special attention was paid to the measurement of Cr(VI) concentration in the contact solution and to the elucidation of the effects of the stabilizing treatment by x-ray photoelectron spectroscopy (XPS). The experimental results indicate that both stabilized and unstabilized CrO₂ particles predominantly release hexavalent chromium when in contact with water. The solubility of freshly stabilized CrO₂ is considerably smaller than that of unstabilized CrO₂, but the difference in solubility diminishes with aged particles. The XPS study indicated that stabilization of CrO₂ particles with a bisulfite solution results in the formation of Cr₂O₃ or a Cr₂O₃-like product on the particle. However, it appears that Cr(III) oxide coating does not uniformly form on all particles.     

Effects of thermal history on the rigid amorphous phase in poly(phenylene sulfide)

The rigid amorphous phase of semicrystalline poly(phenylene sulfide) (PPS) has been studied as a function of thermal history using scanning calorimetry, dielectric relaxation, density, and small-angle x-ray scattering (SAXS). Based on the new heat of fusion of perfect crystalline PPS, which is 26.7±0.8 cal/gram, the weight fraction of rigid amorphous phase is shown to be nearly twice as large as previously reported [1]. The mass fraction of the rigid amorphous phase ranges from 0.24 to 0.42 and is dependent upon thermal treatment. We have taken the approach of assuming a three-phase model for the morphology of semicrystalline PPS consisting of crystalline lamellae, mobile amorphous, and rigid amorphous components. Using this three-phase model, we determine that the average density of the rigid amorphous fraction is 1.325 g/cc, which is slightly larger than the density of the mobile amorphous phase fraction and was insensitive to thermal history. From the SAXS long period, the layer thicknesses of the mobile amorphous phase, rigid amorphous phase, and crystal lamellae were estimated. Only the lamellar thickness shows a systematic variation with thermal history, increasing with melt or cold crystallization temperature, or with decreasing cooling rate.     

Ringing gels: Their structure and macroscopic properties

The phase diagram of the ternary surfactant system which consists of dimethyltetradecylaminoxide, hydrocarbon, and water contains a highly elastic gel phase which borders on the micellarL ₁-phase. This gel phase is transparent, optically isotropic, and shows the ringing phenomena when it is excited to mechanical vibrations. From SANS and light-scattering measurements it is shown that this phase consists of the same spherical microemulsion droplets which are present in the adjacent micellar solution. Even in the micellar solution the droplets are fairly monodisperse and in the SANS scattering functions a second scattering maximum was observed. Both the light scattering and SANS data can be described quantitatively on the basis of hard sphere interactions between the particles. Furthermore, it is shown that elasticity and shear modulus of the gel phase, which were determined experimentally, correlate with the compressibility modulus as calculated from the scattering data. The elasticity modulus and hence the osmotic compressibility modulus are related to the Laplace pressure inside the globules. For the calculation of this pressure it is possible to take the interfacial tension, which is obtained from a dilute micellar solution against the hydrocarbon which is used for the system. The radius of the particles and the hydrocarbon content in the system can be increased when some of the dimethyltetradecylaminoxide is replaced by dimethyltetradecylphosphinoxide.     

Theory of shear-induced crystallization of polymer melts

In the presented model elements of polymer melt rheology and polymer crystallization kinetics are combined. In particular, the proneness of the melt to the special type of crystallization which is characteristic for shear treatment is supposed to emerge only gradually during shear flow. Following Avrami's early ideas on crystal growth, an induction time is introduced. In principle, the model can be applied to any flow and temperature history. The special case of isothermal flow at constant shear rate is covered in greater detail: A favorable comparison is made with experimental results, as published by Lagasse and Maxwell [10].Dedicated to Prof. J. Meissner on the occasion for his 60th birthday.     

Precipitation of surfactant salts III. Metal perfluoroalkanecarboxylates

Precipitation of perfluorocarboxylic acids (n-C₃H₇OOH, n-C₇H₁₅COOH, and n-C₉F₁₉COOH) in aqueous solutions of different metal nitrates (K⁺, Ag⁺, Ca²⁺, Ba²⁺, Zn²⁺, Al³⁺, La³⁺) was studied by solubility and calorimetric measurements. The free energy of precipitation per single surfactant chain was found to depend on the chain length but not on the charge of the reacting cation. It was shown that the precipitation of perfluorocarboxylates of multivalent cations was governed by positive entropy change and a low enthalpic contribution, whereas the soaps of monovalent cations exhibited the opposite behavior. The entropy of precipitation was not affected by the chain length of the surfactants in the presence of monovalent cations, but it increased for cations of higher charge.Supported by the NSF Grant CHE-8619509.This paper is dedicated to Professor Armin Weiss on the occasion of his 60th birthday. One of the authors (E. M.) particularly appreciates many years of cooperation with Professor Weiss in editing Colloid and Polymer Science, as well as in many other scientific interactions.     

Investigations of a series of nonionic surfactants of sugar-lipid hybrids by light scattering and electron microscopy

Sugar-lipid hybrids of the type C_nC_m were prepared by coupling an alkane chain (C_n) with a maltooligosaccharide (G_m) over an amide linkage. Coupling was performed with maltobionolactone (G₂) and n-alkylamine chains C_n withn=8,10,12,14,16, i.e. variation of the hydrophobic part of the molecule, and with hexadecylamine (C₁₆) and different maltooligosaccharides (G_m, m=2,3,4,6). The solution properties of the various products were studied by means of static and dynamic light scattering (LS) and by electron-microscopy (EM).The results may be summarized as follows: If the alkane chain is shorter thann=14, small spherical micelles with a radius of about 3 nm are observed. In time these micelles aggregate further to form increasingly larger spherical clusters which eventually precipitate. Long rod-like micelles form whenn 14. Contour length and chain stiffness were determined by applying theories of semiflexible chains. A qualitative confirmation of the light scattering results, i.e., micelle size and shape, was obtained from electron microscopy.     

Interface stabilization and micelle formation in blends with a block copolymer

The phase separation behavior of ternary blends of two homopolymers, PMMA and PS, and a block copolymer of styrene and methylmethacrylate, P(S-b-MMA), was studied. The homopolymers were of equal chain length and were kept at equal amounts. Two copolymers were used with blocks of equal length, which exceeded or equaled that of the homopolymer chains. Varied was the copolymer contentf. Films were cast from toluene, which is a nonselective solvent. The morphologies of the cast films were compared with the structure of the critical fluctuations in solution, which were calculated in mean field approximation. The axis of blend compositionsf can be divided into parts of dominating macrophase and microphase separation. Above a transition concentrationf _o, all copolymer chains are found in phase interfaces. Belowf _o, part of them form micelles within the homopolymer phases.     

Discussion of craze formation and growth in amorphous polymers in terms of the multiplicity of glass transition at low temperatures

A craze, the typical deformation zone in an amorphous polymer, can be divided into a precraze and a proper craze. A better understanding of the two corresponding formation processes is possible in terms of glass transition multiplicity.The precraze is associated with the molecular mobility in the confined flow zone, which is part of the main transition. The proper craze corresponds to the mobility in the flow transition zone (terminal zone for shear). A negative pressure generated by nonuniaxial stress is considered to be important for the maintainance of the molecular mobility in these zones belowT _g . The behavior of the zones at negative pressure and low temperatures Tg is considered using a pressure-temperature diagram. The fibril structure of crazes is discussed by a defect diffusion model for the proper glass transition; it is correlated with the sequential physical aging of the corresponding frozen structural defects. Typical mode lengths of the molecular mobilities in the different zones are compared with typical craze parameters. The structure of the craze material is considered to result from confined flow processes which cannot percolate because in the main transition the flow is confined by entanglements, and in the flow transition zone the flow is stopped by releasing the negative pressure due to crack propagation.     

Surfactant-free emulsion polymerization of styrene using crosslinked seed particles

The aim of this research was to prepare a monodisperse polystyrene latex without surfactants adsorbed at the particle surface. Conventional polymerization formulations usually lead to large amounts of oligomers. Furthermore, they are characterized by a low reproducibility with respect to particle size. This was overcome by using a seed latex that was crosslinked in order to overcome dissolution in the monomer phase. By adjusting the seed concentration, any desired particle size in the range 0.5–1.2 m could be obtained. The monodispersity was very good.     

Effects of uniaxial stretching and shrinkage on proton spin-lattice and spin-spin relaxation times of isotactic polypropylene

An isotactic polypropylene film was stretched at 120 °C in poly(ethylene glycol) and thermally shrunk at various temperatures. Proton spin-lattice,T ₁, and spin-spin,T ₂, relaxation times were measured using a broad line pulse spectrometer operating at 19.8 MHz in the temperature range 40 °C–100 °C. The temperature ofT ₁ minimum shifts to higher temperatures and the value ofT ₁ minimum increases in magnitude as the stretching ratio is increased. In contrast the temperature ofT ₁ minimum shifts to lower temperatures as shrinkage is increased, whereas the value ofT ₁ minimum increases in magnitude because of the increase in crystallimty during shrinkage. T_2a, the longestT ₁ associated with the mobile amorphous regions, increases during shrinkage, indicating that chain mobility in the amorphous regions increases substantially during shrinkage. It was found that an orientation function of the amorphous regions,f _a, correlates well withT _2a .Presented in part at the 52nd Annual Meeting of the Japan Chemical Society, Kyoto, April 1986.     

Microstructure and lateral diffusion in monolayers of polymerizable amphiphiles

Lipid analogue amphiphilic molecules containing polymerizable units were investigated in monolayers at the air/water interface by using film balance measurements, fluorescence microscopy, and photobleaching techniques. The polymerizable groups (diene-, diyne-, and methacrylate units) were introduced into the hydrophobic alkyl chains or into the polar head of the amphiphilic molecules.In the case of the diene- and diyne-containing compounds the polymerizable units are incorporated into the hydrophobic alkyl chains, enabling them to form a two-dimensional network. Due to the free chain flexibility of the monomers the lateral mobility was comparable to that of saturated lipid analogues and decreases upon polymerization proportionally to the dose of UV irradiation. In addition, fluid/solid phase transitions of compounds with polymerizable groups in the hydrophobic part tend to vanish during the formation of the polymers. However, the direct observation of the growth of polymeric crystalline domains can be followed by using diacetylene lipid analogues.In the case of the methacrylate derivatives the polymerizable unit was coupled to the polar part via a flexible spacer. For these systems the characteristics of the monomeric phase transition are retained after polymerization. However, it shows a significant, strong decrease of the in-plane mobility already in the fluid-expanded phase of the polymer. The quantitative measurements of the lateral diffusion in the monolayers can be correlated with fluorescence microscopic images of their structure.