Der Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline, 6. Mitteilung: Korrelationsanalyse und Ergebnisse

Impact of Chemical and Physical Data on the Practical Properties of Vaseline 6: Correlation Analysis and Results Relationships (linear, log-log, and log-linear) between the data on chemical analysis of structural groups, physical data, and practical properties of 28 different varieties of vaseline have been determined by a digital computer using ALGOL-program. The results are given in two schemes. Two types of vaseline have been found: a) vaselines having low tack, poor oil-binding ability, and a crystalline structure owing to the n-paraffins; b) high tack vaselines that are thixotropic also in sheared state, have good oil binding properties, and form micelles with high molecular weight iso-paraffins. The common methods for physical determination, as described in most pharmacopiae, should be replaced by rheological measurements, dilatometry and determination of oil number. Both sheared and unsheared vaselines should be examined.     

Charakterisierung von ungesättigten Kohlenwasserstoffen der Vaseline und Nachweis des Fehlens carcinogener Verbindungen, 9. Mitteilung: Über den Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline

Characterization of Unsaturated Hydrocarbons of Vaseline and Detection of the Absence of Carcinogenic Compounds 9: Influence of Chemical and Physical Data on the Practical Properties of Vaseline Unsaturated hydrocarbons were found in 28 samples of vaseline tested. Small amounts of polycyclic hydrocarbons were found in ubiquitary amounts. 3,4-benzpyrene was not detected in vaselines. The amount of polycyclic hydrocarbons decreases after sterilization with hot air. By elemental analysis of olefinic hydrocarbons the amount of hydrogen lesser than the saturated compounds can be determined from which the number of double bonds per molecule is calculated. In olefinic fractions of vaselines, which have an average molecular weight between 400 and 820, five to nine double bonds per molecule have been found. Small amounts of nitrogen and sulfur have been detected beside hydrocarbons.     

Der Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline, 1. Mitteilung: Trennung von Vaseline in Substanzklassen mittels chromatographischer Methoden

Impact of Chemical and Physical Data on the Practical Properties of Vaseline 1: Separation of Vaseline in Substance Classes by Chromatographic Methods Twentyeight different vaselines of various qualities were fractionated over a silver nitrate-silica gel column using cyclohexane, carbon tetrachloride/benzene, and acetone/chloroform into saturated hydrocarbons, mono-olefins, which are barely present, and higher unsaturated hydrocarbons. Using a novel urea-silica gel column and chloroform/methanol as solvent, branched chain hydrocarbons and naphthenes are separated from n-paraffins. The separations are monitored by thin-layer chromatography. It was possible, for the first time, to obtain stable urea layers using a solution of sorbitol, and to achieve distinct separation by the incorporation of pyridine to the developing solvent. The analytical results of n-paraffins and of the iso-fraction agreed with the literature, whereas the occurrence of large amounts of unsaturated compounds was surprising.     

Der Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline, 2. Mitteilung: Gel- und gaschromatographische Trennung

Impact of Chemical and Physical Data on the Practical Properties of Vaseline 2: Gel and Gas Chromatographic Separation Molecular weight distribution of hydrocarbons in vaselines and vaseline fractions can be investigated by gel chromatography on polystyrene gel BIO-BEADS SX-1 using toluene as eluting solvent. Since the molecular sieves can be employed at room temperature and as they enable fractionation in the higher molecular region, gel chromatography can serve as an excellent complementary technique to gas chromatography. Experimental conditions for the analysis of vaseline are described.     

Gelchromatographische Abtrennung und Nachweis hochpolymerer Zusätze in Vaselinen 11. Mitteilung: Über den Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline

Gel Chromatographic Separation and Detection of High Molecular Additives in Vaselines 11: Influence of Chemical and Physical Data on the Practical Properties of Vaseline High polymeric substances in vaselines or similar hydrocarbon mixtures, such as lubricating oils, can be separated by gel filtration and identified by infrared spectroscopy and gel chromatography.     

Gelchromatographische Abtrennung und Nachweis hochpolymerer Zusätze in Vaselinen 11. Mitteilung: Über den Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline

Gel Chromatographic Separation and Detection of High Molecular Additives in Vaselines 11: Influence of Chemical and Physical Data on the Practical Properties of Vaseline High polymeric substances in vaselines or similar hydrocarbon mixtures, such as lubricating oils, can be separated by gel filtration and identified by infrared spectroscopy and gel chromatography.     

Charakterisierung von verzweigten Kohlenwasserstoffen der Vaseline und deren Einflüsse auf die Gebrauchseigenschaften als Salbengrundlage, 8. Mitteilung: Über den Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline

Characterization of Branched Hydrocarbons of Vaseline and Their Influence on the Practical Properties of Ointment Bases 8: Influence of Chemical and Physical Data on the Practical Properties From saturated branched hydrocarbons obtained from 18 different qualities of vaseline 10–22% of possibly pure methyl branched hydrocarbons were separated by formation of thiourea adducts and 19–54% paraffin oil were separated by solvent fractionation. The remaining 18–45% soft wax consisted of long chain branched paraffins which strongly influenced the plasticity of vaseline. Viscosity of the oil was correlated with the average molecular weight of the fraction. No relationship was found between viscosity and the proportion of structural groups.     

Gelchromatographische Trennung von verzweigten Kohlenwasserstoffen aus Vaselinen 10. Mitteilung: Über den Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline

Gel Chromatographic Separation of Branched Hydrocarbons from Vaselines 10: Influence of Chemical and Physical Data on the Practical Properties of Vaseline Six different iso-fractions from vaselines were examined for their chemical compositon. The vaseline samples were first fractionated into unsaturated hydrocarbons, n- and iso-paraffins using silver nitrate and urea-silicagel columns respectively. For the determination of chemical fine structure, the iso-fractions were fractionated according to molecular weights by preparative gel chromatography. The individual GPC-fractions were examined by IR-spectroscopy according to H. Luther and H. H. Oelert in order to determine the content of CH₂-groups in long and short chains, methyl groups, naphthenic CH₂-groups and tertiary C-atoms. Large differences between the structural groups were observed between the solid and liquid hydrocarbons within the same vaseline sample. The values found were used to postulate the hypothetical structural formulae.     

Der Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline, 3. Mitteilung: Spektroskopische Strukturgruppenanalyse

Impact of Chemical and Physical Data on the Practical Properties of Vaseline 3: Spectroscopic Analysis of Structural Groups. Spectroscopic methods for the analysis of structural groups of hydrocarbons, according to H. Luther and H. H. Oelert, have been applied to vaselines and iso-fractions derived from them. IR-spectrum gives the amounts of long chain, short chain and naphthenic methylene groups, and methyl and methin groups; nuclear magnetic resonance spectrum yields the amount of protons in methyl, methylene and methin groups. Inspite of differences in origin, vaselines exhibit a rather similar distribution of individual structural components.     

Der Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline, 4. Mitteilung: Physikalische Bestimmungen

Impact of Chemical and Physical Data on the Practical Properties of Vaseline 4: Physical Determinations The physical methods prescribed in various pharmacopiae have been tested on 28 different samples of vaseline, and the relative standard deviations have been determined. Solidification point, determined on rotating thermometer is found to be very well suited for the determination of melting behaviour. Rheological properties of the vaselines have been investigated in a Brookfield rotary viscometer using sheared and unsheared samples. The area of histeresis curve, as determined by planimetry, and the comparison of sheared and unsheared vaselines are well-reproducible parameters which provide valuable information. Dilatometry has been employed for the determination of solids in vaseline as a function of temperature. Surface tension of vaseline layers has been determined by measuring the angle of wetting of water droplets. Oil number is determined in a most reproducible manner by gravimetry in laboratories having constant atmospheric conditions. Quotient of oil numbers of sheared and unsheared vaselines is very significant criterium for their quality.     

Der Einfluß chemischer und physikalischer Meßdaten auf die Gebrauchseigenschaften von Vaseline, 5. Mitteilung: Messung der Gebrauchseigenschaften

Impact of Chemical and Physical Data on the Practical Properties of Vaseline 5: Measurement of Practical Properties Following practical properties of 28 different varieties of vaseline have been investigated: tack, maximum oil uptake as determined from rheological data, water number, stability of W/O and O/W emulsions, and pigment uptake. From the viewpoint of practical applications, the properties examined were the extent of soaking of medical bandage, ability to anoint and water penetration on human skin. The data obtained should serve for correlation analysis to be reported in 6th communication of this series.     

Einfluß der Gruppenkomponenten auf die Eigenschaften von Estermontanwachsen

Influence of Group Components on the Properties of Montana Ester Waxes The group of wax esters and hydrocarbons was separated from the refined wax R by means of ion exchange on Wofatit SBW and column chromatography on silica gel. A part of the wax acids obtained was esterified with ethyleneglycol. Twenty wax systems having various compositions were prepared from wax acid glycolester and hydrocarbon group components. The wax systems were investigated for drop point, characteristic values, density, electrostatic properties, penetration, flow point, and flow curve. Furthermore, the formation of water emulsions was studied with these wax systems. Relationships between the composition of group components and definite physical and chemical characteristics were established.     

Eine objektive Bestimmung der Zügigkeit von Vaselinen und Salbengrundlagen mit einem modifizierten Laray-Tackmeter

An Objective Method for the Determination of Tack of Vaselines and Ointment Bases Using a Modified Laray-Tackmeter The tack of ointments, especially vaselines, can be determined objectively using a modified Laray-tackmeter which measures the tangential shearing force required to separate two adjacent films of the ointment. Thickness of the layer and optimum experimental conditions as well as their reproducibility (ca. 4-5%) are given. Temperature function of the tack follows the Arrhenius equation. Applications of this method are shown in the analysis of vaselines having varying tack. Vaselines, containing high polymers as additives, dust from the rolls, and are thus identified. While examining vaseline fractions, high tack of the unsaturated fraction was noticed. It is shown that empirical tack, and the tack determined with 99% probability correlate with each other; also correlations are found with useful practical properties, such as oil number or plastic viscosity of sheared vaselines. The measurement of tack in ointment bases revealed the influence of hydrocarbons; fatty alcohols had no action. In O/W emulsions, the tack of the vaseline employed completely disappears.     

Der Einfluß von Tensiden auf physikalische Eigenschaften von Keratinfasern

Influence of Surfactants on the Physical Properties of Keratin Fibres It could be proved by stress-strain tests that keratin fibres are more easily stretched in aqueous solutions of various ionic surfactants than in pure water. This effect can be further intensified in solutions of acidic and alkaline pH values. The extent of weakening of the fibre is dependent upon the chain length of the surfactant and the degree of adsorption. These effects are fully reversible by rinsing with distilled water. However, a splitting of the cystine bonds occurs in strongly alkaline solutions. The damage on keratin fibres caused by aqueous solutions of ionic surfactants is explained by the opening of hydrophobic bonds.     

Einfluß der Metallseifen auf die rheologischen Eigenschaften von lipophilen Grundlagen

Influence of Metallic Soaps on Rheological Properties of Lipophilic Bases Influence of metallic soaps on the rheological properties of lipophilic suppository bases was determined. The investigations revealed that rheological properties of suppository bases are considerably altered by the addition of metallic soaps. Alterations in rheological properties are determined from the ratio of solid to liquid components.     

Der Einfluß von Netz- und Hydrophobierungsmitteln auf die Eigenschaften von Zementmörtel

Influence of Wetting and Hydrophobing Agents on the Properties of cement Mortar The relationships between the water requirement of cement mortar, its pore volume and resistence to pressure and water, and the chemical composition of wetting and hydrophobing agents added have been studied. It was found that the rigidity and absorbing capacity are dependent not only upon the density and pore volume of mortar but also upon the chemical structure of the additives. Inspite of reduced density and increased pore volume, it is possible to attain a rigidity of structure and low water absorbence by employing a definite ratio between the hydrophilic and lyophilic ligands in the molecule of the additive.     

Einfluß der chemischen Struktur auf das Luftabscheidevermögen und die hydrolytische Stabilität von Estern

Influence of the Chemical Structure in Regard to the Air Release Properties and the Hydrolytic Stability of Esters Esters, based on fatty chemical basis, are of great importance for the lubricant industry as efficient, biodegradable basestocks and additives. The structure possibilities and synthetic variations of ester oils are described. Basic datas are presented inclusive application areas. Parameters like air release properties and hydrolytic stability possess a central function in special applications like hydraulic fluids or compressor lubes. Oil dispersed air bubbles influence the compressibility and can cause disturbances in oil containing systems. Esterhydrolysis by water are followed by precipitation, decompositions and increased corrosivity. The determination of the air release according DIN 51 381 and the hydrolytic stability leanded against ASTM D-2619 are explained. A great number of esters based on primary and polyhydric alcohols in combination with branched and unbranched, saturated and unsaturated mono- and dicarboxylic acids were tested. Structure-effects rules were fixed in dependence of viscosity, iodine value, branching degree and carbon chain length in order to improve the choice of esters for synthetic oils.     

Einfluß von Wachsen auf Haft- und Gleitreibung

Influence of Waxing on Adhering and Sliding Friction A new method has been developed for determining the adhering and sliding friction. By this method, the influence of the films of caring agents on the nonskid properties can be determined very accurately. Novel finding of the present work is that by multiple measurements and mathematical-statistical evaluation valid statements can be made on the nonskid properties of floors. Furthermore, it could be shown that, in the rule, ester waxes have a positive effect on the nonskid properties.     

Der Einfluß von Anion- und Kationtensiden auf die chemische Reaktionsfähigkeit von Wolle

Influence of Anionic and Cationic Surfactants on the Chemical Reactivity of Wool The alkaline degradation of cystine in wool is diminished by anionic detergents and increased by cationic detergents. The reaction with sulphite is influenced in a similar manner. In acidic media, the opposite effect is exerted by ionic detergents on the acid hydrolysis of wool peptide bonds; hydrolysis is enhanced by anionic detergents and diminished by cationics. Nonionic detergents are without any effect on the chemical reactivity of wool. The results are explained in terms of changes in electrical charges on the fibre surface, due to adsorption of detergent ions.     

Einfluß von Additiven und Verunreinigungen auf Kristallisationsprozesse

Influence of additives and contaminants on crystallisation processes. The presence of additives and contaminants in a crystallising solution can have a considerable influence on the crystallisation properties of the products, such as nucleation and growth kinetics, agglomeration or dispersion of the crystals, and the incorporation of foreign ions into the crystal lattice. These influences are caused by various mechanisms, depending upon the type of additive or contaminant. Tailor-made and multifunctional additives are distinguished. Trace amounts of metal ions can also modify the kinetics of crystallisation. The metal ions can be incorporated to a greater or lesser extent in the crystal, depending upon thermodynamic and kinetic factors.