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  • 1985-1989
  • 1975-1979  (515)
  • 1960-1964
  • 1976  (515)
  • Physics  (492)
  • pharmacokinetics
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 9 (1976), S. 327-332 
    ISSN: 1432-1041
    Keywords: Antipyrine ; pharmacokinetics ; half-life ; blood ; plasma ; saliva ; individual variation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A previously described GLC method has been modified and applied to measurement of antipyrine levels in plasma, blood and saliva of man following administration of a single oral dose (10 mg/kg). The levels in blood and saliva were comparable to those in plasma at every time studied. The half life of antipyrine determined in blood, plasma or saliva in any given individual was similar. The intersubject variation in half-life was about two-fold (n=5). Antipyrine levels in saliva were not affected by the rate of saliva flow when collections were made continuously for 20 minutes. This study has demonstrated that kinetic data about antipyrine comparable to that from plasma may also be obtained from readily accessible tissue fluids, such as saliva and capillary blood.
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  • 2
    ISSN: 1432-1041
    Keywords: Chlorthalidone ; diuretics ; drug plasma concentration ; protein binding ; red blood-cell concentration ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A gas chromatographic method has been employed to determine chlorthalidone in plasma and whole blood after therapeutic doses. Radioactively labelled chlorthalidone was used for in vitro studies of the uptake of chlorthalidone from plasma by red blood cells. Chlorthalidone was markedly concentrated in red cells and as a compartment they would account for at least 30% of total drug in the body after multiple doses. The ratio between the plasma and red cell concentration of chlorthalidone varied between individuals. After a single oral dose of 50 mg in 6 healthy volunteers chlorthalidone was eliminated with a half-life of 51 to 89 hours. The apparent volume of distribution varied between 3 and 13 1/kg and the clearance between 53 and 145 ml/min. The mean steady-state plasma concentrations during treatment with a standard dose of 50 mg daily (n=10) varied 5-fold between individuals. During the steady state approximately 50% of the daily dose was excreted unchanged in the urine during 24 hrs. The plasma levels observed in patients were higher than those predicted from the single oral dose studies in healthy volunteers.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 9 (1976), S. 367-372 
    ISSN: 1432-1041
    Keywords: Sotalol ; β-adrenoceptor blocking drugs ; exercise tachycardia ; efficacy ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The effects of sotalol after oral administration were measured on the tachycardia induced by strenuous exercise in normal subjects. Plasma sotalol levels were also determined. The oral administration of sotalol (50, 100, 200 and 400 mg) to 6 subjects produced a progressive reduction in the tachycardia induced by severe exercise. This was similar to the effects of 25, 50, 100, 200, 400 and 800 mg given to different subjects. Each increase in sotalol dose produced a successively greater reduction in exercise tachycardia. This did not appear to be maximum even with 800 mg. Oral sotalol was rapidly absorbed and produced peak blood levels in 2 – 3 hours. The plasma levels of sotalol measured 2 hours after the oral administration of 25 to 800 mg showed never more than a six-fold variation between different subjects. The half-life of sotalol in plasma was 12.7 ± SE 1.6 hours. There was a significant correlation between the logarithm of the plasma sotalol concentration and the percentage reduction of exercise heart rate. It is concluded that the oral administration of sotalol either once or twice daily (depending on dose level) will provide satisfactory 24-hour blockade of β-adrenoceptors.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 9 (1976), S. 443-450 
    ISSN: 1432-1041
    Keywords: Cyclobarbital calcium ; pharmacokinetics ; plasma concentration ; relative bioavailability ; oral administration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics and relative bioavailability of cyclobarbital calcium have been studied after oral administration of Phanodorm, of tablets according to the Formularium Nederlandse Apothekers (1968; FNA), and an aqueous solution. Six healthy volunteers participated in the investigation on three occasions and each received the three preparations. The dose administered was 300 mg cyclobarbital calcium. Plasma concentrations of cyclobarbital were determined at regular intervals. Absorption from the three preparations was rapid and was faster from the solution. Peak concentrations were usually attained within 1 h. The elimination of cyclobarbital could be described by a single first-order process with an average half-life of 11.6 h (range 8 – 17 h). There was little intra-subject variation of the half-life. Relative bioavailability for each volunteer was estimated by comparing the areas under the plasma concentration curves. The FNA-tablets and Phanodorm exhibited similar bioavailability, whereas the average bioavailability of the solution was 78% of that of FNA-tablets; the reason for this unexpected finding is unknown. It was concluded that cyclobarbital cannot be regarded as a uniformly suitable drug for the treatment of insomnia. The long half-life that was apparent in some of the volunteers (15 – 17 h) creates a substantial risk of residual effects on the following morning. In principle, however, the calcium salt of cyclobarbital may be used for induction of sleep, because of its rapid absorption.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 251-256 
    ISSN: 1432-1041
    Keywords: Sisomicin ; pharmacokinetics ; bioavailability ; two-compartment analysis ; man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of sisomicin, a new single component aminoglycoside antibiotic related to gentamicin c1a, were determined in four healthy volunteers after intravenous and intramuscular administration of a 1 mg/kg dose. The elimination profile of this antibiotic follows two-compartment model kinetics after I.V. administration. The fast (α) and slow (β) disposition rate constants averaged 0.072 and 0.004 min−1, respectively. The volume of distribution at the steady-state averaged 0.185 liters/kg which approximately corresponds to the volume of extracellular space. The physiological availability of an intramuscular dose appeared to be complete. A method of administration adapted to the kinetic properties of the drug is proposed.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 311-317 
    ISSN: 1432-1041
    Keywords: Hydralazine ; instability of impaired renal function ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Following a single 50 mg dose of hydralazine (Apresoline®) in 13 patients with impaired renal function, a decrease in glomerular filtration rate (GFR) was correlated with an increase in serum half-life (T1/2) of the drug (r=−0.69; p〈0.01). The T1/2 was 15.8 h in one patient with a GFR of 16 ml·min−1, as compared to a T1/2 of 1.7–3.0 h found previously in 16 healthy volunteers. In 49 patients on long-term antihypertensive treatment with hydralazine, the ratio between the minimum steady-state drug concentration and the daily dose of hydralazine (C SS min : Dose) increased as the GFR decreased. This accumulation of the drug was particularly evident in patients with a GFR less than 30 ml·min−1 (r=−0.63; p〈0.01; n=19). As renal excretion of unchanged hydralazine is generally regarded as unimportant, the slower elimination rate in chronic renal failure was probably caused by a slower rate of metabolic conversion. It was found, however, that the renal excretion of hydralazine could easily have been underestimated, as only 12.7% of an initial hydralazine concentration of 200 ng·ml−1 in urine could be recovered after storage of the samples at room temperature for 24 h.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 325-330 
    ISSN: 1432-1041
    Keywords: Flutiorex ; pharmacokinetics ; sex ; anorectic agent ; sympathetic stimulation ; CNS stimulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The effects of flutiorex, a new anorectic agent, and of a placebo on food intake and the activity of the sympathetic and central nervous systems have been compared in a double blind trial in two groups of healthy volunteers, one of five males and the other of five females. Flutiorex 20 mg orally had a significant anorectic effect both in males and females, the observed reduction in food intake being 34.0 and 27.5%, respectively. It caused α-adrenergic stimulation (blood pressure and pupil diameter) and central nervous system excitation (critical flicker frequency), both of which were more marked in males than in females. Flutiorex was better tolerated by women than by men. Measurement of the blood level of flutiorex and its de-ethylated metabolite, norflutiorex, showed that both compounds were detectable in four of the five male subjects, but in only one of the five females. Sex-linked differences in the pharmacokinetics of flutiorex may explain the greater intensity of its effects in males.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 343-347 
    ISSN: 1432-1041
    Keywords: Methaqualone ; hypnotic ; pharmacokinetics ; combination formulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Concentrations of methaqualone have been measured in the serum of five male human subjects receiving five consecutive evening doses of a combination formulation containing methaqualone (250 mg), carbromal (300 mg) and benactyzine (0.33 mg) in each tablet. After administration of the first dose, mean peak serum concentrations of methaqualone (1.2 µg/ml) occurred at 3 h. After obtaining peak levels, mean concentrations of methaqualone declined rapidly during the next 6 h and there-after more slowly during the next 18 h. After administration of the last (fifth) dose, mean peak serum concentrations of methaqualone (1.9 µg/ml; 1.5 µg/ml above the predose level) occurred at 2 h. After attaining peak levels, mean concentrations of methaqualone declined rapidly during the next 6 h, and thereafter more slowly, with a half-life of approximately 10 h. Mean concentrations of methaqualone in serum samples 24 h after the second, third, fourth or fifth doses were not significantly different (0.3 µg/ml – 0.6 µg/ml) during this period of dosing. This suggests that significant accumulation of methaqualone in the serum did not occur during a period of five consecutive evening doses of the combination formulation.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 257-262 
    ISSN: 1432-1041
    Keywords: Anti-inflammatory and analgesic drug ; indoprofen ; pharmacokinetics ; bioavailability ; man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In a pharmacokinetic study of the new analgesic and anti-inflammatory drug indoprofen, plasma levels and urinary excretion were determined in four healthy volunteers after 100 mg and 200 mg iv, and after 100 mg (capsules) and 200 mg (tablets) oral doses. After iv administration, the mean biological half-life (t1/2 β) was about 2 h (range 1.4 to 3.2 h). The apparent volume of distribution Vdβ ranged between 11 to 17 % of body weight, indicating its limited extravascular distribution. Most of the drug was excreted in urine as glucuronide and a smaller proportion as unchanged indoprofen: the 24 h urinary excretion of these compounds accounted for 67 to 95 % of an iv dose. Peak plasma levels occurred between 30 and 120 minutes after oral administration of 100 mg as capsules or 200 mg as tablets. The mean biological half-life was about 2 h, as after iv administration. The bioavailability of oral doses was assessed using both plasma levels and urinary excretion data. The absorption of capsules and tablets was practically complete, that of the former being faster.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 25-29 
    ISSN: 1432-1041
    Keywords: Digoxin ; exchange transfusion ; pharmacokinetics ; neonates ; 86Rb assay
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary By means of an86Rb-uptake inhibition assay, changes in the plasma concentration of digoxin and the amount of the glycoside removed during exchange transfusion have been studied in two newborns. For comparison, the exchange procedure was simulated by a computer on the basis of a two-compartment open model and available pharmacokinetic constants. A rapid decrease in plasma digoxin concentration during exchange transfusion was found when the glycoside was administered intravenously or intramuscularly within 60 min before the procedure. The amount of digoxin removed by the exchange was less than 6 per cent of the given dose. Computer simulation of the procedure also showed removal of only a minor amount of digoxin. It is concluded that the decrease in plasma concentration and the removal of only a small amount of glycoside by the exchange transfusion can be attributed mainly to extensive tissue distribution of digoxin. The results imply that replacement of digoxin after an exchange transfusion seems unnecessary.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 121-126 
    ISSN: 1432-1041
    Keywords: Diazepam ; pharmacokinetics ; subchronic dosage in man ; desmethyldiazepam
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In seven healthy male volunteers the effects of the pattern of dosing on the pharmacokinetics of diazepam have been studied. A cross-over design was employed that consisted of three parts: a single intravenous dose (0.1 mg/kg), and oral dosing (10 mg/day) for six days followed by an intravenous bolus (0.1 mg/kg) on the seventh day, followed by re-examination of a single intravenous dose after diazepam (D) and its major metabolite desmethyldiazepam (DD) had been completely eliminated. Plasma levels of D and DD were monitored by a specific, sensitive GLC-method. In younger patients (n=5, age 29 – 35 years) the elimination half-life, T1/2 (β), of D was 33.9±10.6 h (mean±S.D.) after the single dose. The control study gave an almost identical result (35.7±12.1). After subchronic dosage in all patients T1/2 (β) showed a modest but significant prolongation (paired t-test p〈0.01) to 52.9±17.4 h. It was caused by a significant decrease (p=0.016) in total plasma clearance ( $$\overline {\user1{Cl}} $$ ), from 26.0±10.8 ml/min to 18.2±7.0 ml/min. Older patients (age 43–60 years) showed the same phenomenon. Blood/plasma ratios remained constant indicating no change in protein binding. Biliary excretion of D was measured in five patients with a T-tube. Only negligible amounts (0.3–0.4%) of administered D were excreted within 3 days after subchronic dosage, which demonstrates a lack of enterohepatic cycling of D. After multiple administration of D, there was accumulation of DD to levels approximately five times higher than after a single dose. The possibility that the slower elimination of D after subchronic treatment might be caused by DD was also supported by experiments in dogs and rabbits. After pretreating rabbits with DD and maintaining a high DD plasma level, there was prolongation of T1/2 (β) from 2.7 h to 5.2 h, with a corresponding decrease of $$\overline {\user1{Cl}} $$ from 101.6 ml/min to 23.4 ml/min. Similar results were obtained in dogs. It is concluded that the disposition of D is altered by subchronic use and may be regulated by the plasma DD concentration.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 183-187 
    ISSN: 1432-1041
    Keywords: Hydralazine ; bioavailability ; pharmacogenetics ; first pass effect ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary After oral administration of a single 50 mg dose of hydralazine (Apresoline®), the serum half-life (T1/2) and bioavailability (AUC0−∞) were assessed in 16 healthy volunteers. The half-life was 2.57±0.14 h (S.E.) in 10 slow acetylators of sulphadimidine, and 2.18±0.15 h in 6 fast acetylators (difference not statistically significant). AUC0−∞ was significantly higher in slow acetylators, at 1.04±0.10 µg·hour·ml−1, compared to 0.66±0.12 µg·hour·ml−1 in the fast acetylators (p〈0.025). Treatment with Apresoline® 25 mg tid produced minimum serum concentrations at steady-state of 57.3±7.3 ng·ml−1 and 33.4±4.2 ng·ml−1 in 8 slow and 5 fast acetylators, respectively (p〈0.05). The corresponding maximum concentrations were 228.8±20.3 ng·ml−1 and 147.6±15.0 ng·ml−1 in slow and fast acetylators, respectively (p〈0.025). First-pass metabolism of hydralazine could explain the difference in bioavailability of the drug between fast and slow acetylators, without any corresponding difference in the elimination rate of the drug in the post-distributive phase.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 337-341 
    ISSN: 1432-1041
    Keywords: Amitriptyline ; pharmacokinetics ; intravenous infusion ; two compartment model ; biological half-life
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Amitriptyline was given to four male volunteers by constant rate intravenous infusion. Blood samples were collected before, during and at various times after the infusion for estimation of the serum concentrations of amitriptyline. The level of nortriptyline never reached a detectable level. A two compartment open model was shown to be applicable to the data obtained. The meaning of the parameters obtained by a non-linear, least squares curve fitting procedure is discussed and the values are compared to those recently published for nortriptyline. The calculated biological half-life of amitriptyline was about 17 hours, a figure which differs considerably from previously calculated values for volunteers, but is in accordance with some newer results from patients.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 55-58 
    ISSN: 1432-1041
    Keywords: Penicillin V ; bioavailability ; pharmacokinetics ; dose ranging
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary An absorption study was performed in ten healthy volunteers to test the bioavailability of various doses of two penicillin V-K preparations: Isocillin® (Hoechst AG, Federal Republic of Germany), — tablets of 600 000 and 1.2 Mega U; V-Cillin® (Eli Lilly, USA), — tablets of 200 000, 400 000 and 800 000 U. The serum concentrations and elimination of the active substance in urine were measured for six hours after administration. Independently of the source of the preparation, a strict linear relation between the dose and the area under the serum curve (AUC), or between the dose and the urinary elimination, was demonstrated by regression analysis. The dose-dependent increase in the AUC was highly significant (p〈0.01) in the range tested, i.e. between 200 000 and 1.2 Mega U. The relative elimination of active substance in urine lay within narrow limits for all doses (35.7–41.3%). Thus, both compounds proved to have the same bioavailability.
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  • 15
    ISSN: 1432-1041
    Keywords: Ampicillin ; bioavailability ; pharmacokinetics ; branded products ; proprietary preparations ; capsule formulation ; tablet formulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics and bioavailability of three different brands of ampicillin were studied in 10 volunteers. After intravenous administration ampicillin can be described adequately by a two-compartment open pharmacokinetic model. The half-life during the α-phase was 9 min and the β-half-life was in the range 50–60 min, independent of the mode of administration. Absolute bioavailability was determined from the ratio of the areas under the serum concentration curves obtained after oral and intravenous administration of equal doses. Bioavailability was also estimated by analysis of variance. The results indicated absolute availability of the three products of 39–54%. One of the products, a capsule formulation, showed a significantly lower bioavailability than the others, which were tablet formulations.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 263-271 
    ISSN: 1432-1041
    Keywords: Butobarbital ; pharmacokinetics ; plasma concentration ; oral administration ; accumulation ; enzyme induction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A method is described for the assay of therapeutic levels of butobarbital (5-ethyl-5-n-butylbarbituric acid) in human plasma, which involves a single extraction step followed by gas chromatography with alkali flame ionization detection. The pharmacokinetics of butobarbital were studied in five healthy volunteers after oral administration of 200 mg. Plasma concentrations were determined at regular intervals up to 96 h and the data were fitted by non-linear, least squares regression analysis according to one-compartment kinetics. The average lag time was 0.11 h and the absorption half-life 0.21 h. The elimination half-life varied from 33.6 to 41.5 h with an average of 37.5 h. Four of the volunteers participated in a study of multiple dosing (every 24 h) during which substantial accumulation of butobarbital was observed. The elimination half-life after termination of drug administration had decreased to about 20–25% of its initial value, probably because of enzyme induction. It was concluded that butobarbital could not be regarded as a suitable drug for treatment of insomnia, since CNS depressant effects were likely to persist into the following day. Repeated administration of butobarbital should be avoided and its incidental use restricted to patients who require day-time sedation.
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 293-295 
    ISSN: 1432-1041
    Keywords: Bendroflumethiazide ; diuretics ; GLC ; thiazides ; plasma level ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A GLC method for determination of bendroflumethiazide has been developed, using extractive methylation. Cyclopenthiazide was used as internal standard. The maximal plasma concentration (56–107 ng/ml) after bendroflumethiazide 10 mg given orally to four healthy volunteers was seen at 2–2.5 h. On the slope between 4 and 10 h T1/2 averaged 2.7 h.
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  • 18
    ISSN: 1432-1041
    Keywords: Diabetes mellitus ; drug interaction ; phenprocoumon ; pharmacokinetics ; pharmacodynamics ; sulphonylureas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The influence of various antidiabetic treatments on the kinetics and efficacy of a single oral dose of 12 mg phenprocoumon were studied in 71 hospitalized patients, 58 with adult-onset diabetes mellitus and 13 non-diabetic aged patients, and 13 healthy young volunteers. Treatment for one week or longer with insulin or the antidiabetic sulphonylureas tolbutamide, glibenclamide or glibornuride, altered neither the plasma level (1.29 – 1.40 µg/ml at zero time) nor the half-life of phenprocoumon (5.2 – 6.8 d) compared to treatment by diet alone. The mean half-life of phenprocoumon was significantly shorter in non-diabetic aged patients (4.2 d) than in diabetic patients of the same age (5.1 – 6.8 d), or in young healthy volunteers (5.7 d). The efficacy of a single dose of phenprocoumon (maximal reduction of Quick-values by 34 – 47% after 48 to 72 hrs) in diabetic patients treated with diet, or diet and antidiabetic drugs, was the same as in non-diabetic aged patients. In healthy young volunteers phenprocoumon was half as effective as in aged patients.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 10 (1976), S. 63-68 
    ISSN: 1432-1041
    Keywords: Phenazone ; pharmacokinetics ; injuries ; surgery ; operation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The elimination rate of phenazone after a single oral dose has been studied before and after elective operations. In a group of patients with different illnesses the elimination rate was increased on the fourth to seventh days after operation but was unchanged on the second and third days. The change in elimination rate was highly significant in a standardized group of nine patients with a ligament injury in one knee studied on the fourth or fifth postoperative day. Possible reasons for the changes are discussed.
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Journal of pharmacokinetics and pharmacodynamics 4 (1976), S. 199-230 
    ISSN: 1573-8744
    Keywords: disopyramide ; antiarrhythmic ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pharmacokinetics of the antiarrhythmic disopyramide, 4-diisopropylamino-2-phenyl-2-(2-pyridyl)butyramide phosphate, and its monodealkylated metabolite were investigated in seven volunteers after intravenous (1 and 2 mg/kg) and oral (3 and 6 mg/kg) administration. Unchanged drug (52%) and the monodealkylated metabolite (25%) were renally excreted on intravenous administration. The pharmacokinetics of disopyramide were first order and dose independent only when referenced to the drug not bound to plasma proteins since this binding was dose dependent. The apparent half-lives of the α and β phases on intravenous administration were 2 min and 4.5 hr, respectively. The apparent volumes of distribution of the central and peripheral compartments, referenced to unbound disopyramide in the plasma, were 9 and 80 liters, respectively. The half-life of absorption of oral aqueous disopyramide phosphate was 30 min with a lag time of 16 min and an apparent first-pass metabolism of 16% of the absorbed dose, consistent with the hepatic efficiency of 14%. The renal and metabolic clearances were 125 and 111 ml/min, respectively. Graphical and computer analysis of the plasma and urine data showed dose-independent first-order pharmacokinetics of plasma unbound drug in a two-compartment-body model to give two metabolites and a first-pass transformation of a fraction of the oral dose. The absorption efficiency of unchanged drug was 83%.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Journal of pharmacokinetics and pharmacodynamics 4 (1976), S. 337-353 
    ISSN: 1573-8744
    Keywords: bioavailability ; pharmacological data ; pharmacokinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The use of data deriving from monitoring the time variation of the intensity of pharmacological effect(s) following dosing can often present an advantageous alternative to the more conventional approach of using chemical or radiological assay of blood and/or urine level data for bioavailability evaluations of drug products: bioavailability studies can be performed with drugs where no assay exists. A relatively simplified discussion of the general theoretical principles on which the use of pharmacological data is based and a stepwise description of the approach for its routine application in bioavailability studies are presented. Approaches for computing rates and extents of drug bioavailability vs. time profiles on analog and digital computers are qualitatively described and quantitatively presented in a subsequent report. The concept of preabsorption (gastrointestinal bioavailability) is introduced and biophasic availability of drugs to local sites of action is discussed.
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  • 22
    Electronic Resource
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    Springer
    Journal of pharmacokinetics and pharmacodynamics 4 (1976), S. 355-375 
    ISSN: 1573-8744
    Keywords: deconvolution ; bioavailability ; pharmacokinetics ; modeling ; pharmacological data
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Mathematical expressions and approaches to the computation of rates and extents of drug bioavailability for implementation on analog and digital computers are derived. The equivalency of expressions derived on the basis of assuming compartment models to an approach based on using experimentally determined weighting functions is demonstrated. The relative merits of the two techniques are discussed: their application for use with temporal pharmacological data is emphasized. The applicability of the computational techniques to determining the availability of drugs at local sites of action (biophasic availability) and to computing preabsorptive drug release into the gastrointestinal contents (gastrointestinal bioavailability) is pointed out. An approach to computationally predicting in vivo blood level or pharmacological response vs. time profiles from in vitro dissolution testing results is presented and its limitations are discussed.
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  • 23
    ISSN: 1573-8744
    Keywords: pharmacokinetics ; compartmental model ; phenol red ; phenol red glucuronide ; dogfish (Squalus acanthias)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A flow-limited multicompartment model simulates the distribution and disposition of phenol red in the dogfish after intravenous administration. Glucuronide conjugate, as well as parent compound, was found in urine and bile, but not in plasma, kidney, or liver tissue. An apparent 4-hr lag in phenol red appearance in the gall bladder was simulated using two stirred tanks connected in series to represent the bile ducts. The model should facilitate use of the dogfish in pharmacokinetic studies of drugs, environmental contaminants, and other xenobiotics.
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  • 24
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 11-27 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fluorescence anisotropy decay experiments are described for polystyrene in various ethylacetate-tripropionin mixtures. Decay curve trends agree with the proposed theoretical autocorrelation function. Study of the effects of viscosity shows that the mean relaxation time varies according to a nonlinear law for low viscosities and that the relaxation time θ, reflecting the effects of the possible departures from the motions permitted by an ideal tetrahedral lattice, obeys a law of the type: θ = α + bη. Furthermore, the effects of the direction of the fluorophore transition moment are examined.
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  • 25
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1-10 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scattering law S(k,w) for dilute polymer solutions is obtained from Kirkwood's diffusion equation via the projection operator technique. The width Ω(k) of S(k,w) is obtained for all k without replacing the Oseen tensor by its average (as is done in the Rouse-Zimm model) using the “spring-bead” model ignoring memory effects. For small (ka\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} ≪ 1) and large (ka ≫ 1) values of k we find Ω = 0.195 k2/β α η0 \documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} and Ω = k2/βξ, respectively, indicating that the width is governed mainly by the viscosity η0 for small k values and by the friction coefficient ξ for large k values. For intermediate k values which are of importance in neutron scattering we find that in the Rouse limit Ω = k4a2/12βξ. When the hydrodynamic effects are included, Ω(k) becomes 0.055 k3/βη0. Using the Rouse-Zimm model, it is seen that the effect of pre-averaging the Oseen tensor is to underestimate the half-width Ω(k). The implications of the theoretical predictions for scattering experiments are discussed.
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  • 26
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 437-449 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The luminescence of 1,2-polybutadiene was measured during and following irradiation with 1.4-MeV electrons at 90 °K. Measured under isothermal conditions, the light intensity at first increases sharply on start-up of irradiation, and then reaches a plateau after several seconds. The equilibrium value was found to be linearly dependent on the dose rate employed. The postirradiation luminescence decay measured at 90°K follows second-order kinetics.The light emitted by the irradiated sample during warm-up to room temperature is characterized by the appearance of four intensity maxima at 118, 168, 223, and 261 °K. The first three peaks are attributable to the onset of local motion, whereas the peak at 223 °K is caused by the long-range motion occurring at the glass-to-rubber transition. A preirradiation of the polymer in vacuo causes an increase in these four peaks as well as the formation of a new maximum at 143 °K.Intermittent exposure of the irradiated sample to light of wavelengths λ 〉 450 nm causes the isothermal luminescence decay to be interrupted by a burst of light emitted by the sample during and shortly following the light exposure. This treatment also results in considerably reduced intensity maxima during warm-up to room temperature. An interpretation of the findings reported is given on the basis of reactions involving primary and secondary transient species produced during irradiation and on the molecular parameters of the polybutadiene.
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  • 27
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 401-414 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic piezoelectric stress constant e*25 of drawn films of poly(γ-methyl D-glutamate) (PMDG) cast from solutions in α-helix-promoting solvents 1,2-dichloroethane (DCE) and chloroform and from the nonhelicogenic solvent dichloroacetic acid (DCA) was measured from -180°C to 200°C at 110 Hz. The drawn and annealed films cast from chloroform show a small peak for the real part of piezoelectric stress constant -e′25 in the temperature range of the mechanical α2-crystalline relaxation, which is caused by the distortion motion of the backbone chain of the α-helix. On the other hand, drawn films cast from DCE show the peak of the real part of the piezoelectric stress constant, whose magnitude decreases in the range of the mechanical α1-crystalline relaxation or the β-relaxation processes, which were previously ascribed, respectively, to mutual slipping of α-helices and to the micro-Brownian motion of disordered regions. Also, -e′25 becomes virtually zero near 180°C where the α2-relaxation is located. These results suggest that the polarization change induced by applied strain is caused by distortion of the backbone chains in the α-helix. Near 0°C, the temperature range of the side-chain mechanical relaxation, -e′25 exhibits a marked peak both for films cast from chloroform and from DCE. The maximum value of -e′25 and the orientation function of the α-helix axis are linearly related and extrapolation of -e′25,max to unit orientation function gives 1.3 × 104 cgs esu which corresponds to 2.4 Debye per residue. This value corresponds reasonably to the value of 3.71 Debye for the permanent dipole moment of NHCO bond if the correction for crystallinity is made. This result also indicates the piezoelectric properties of PMDG arise from distortion of the backbone chain of the α-helix induced by applied strain.
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  • 28
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 955-957 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 29
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 941-954 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical model developed in an earlier paper describes the experimental x-ray profiles of equatorial nylon-6 reflections in terms of Pearson VII functions. The present paper deals with the physical aspects and interpretations of the interrelations of the parameters obtained and the relation between these parameters and the results of other types of measurements. It was found that the growth of the crystallites perpendicular to the chain axis is not isotropic, the strongest growth being in the direction of the hydrogen bonds. Growth and perfection of the crystallites are found to be highly correlated. Large crystals are related to short distances between the planes containing the hydrogen bonds and so to densely packed, i.e., perfect unit cells. This correlation forms the basis for the observed similarity between our quantification technique and the method of the crystal perfection index introduced by Statton. Curve resolution, however, makes the method better applicable for poorly crystallized samples. Comparison of the results with those of small-angle x-ray scattering gave a high degree of consistency with respect to the determined crystal size. In the literature mention is made of a relation between the dimensions and the melting point of the crystals; this relation is confirmed by comparing the appropriate x-ray parameters with DTA results of methoxymethylated nylon 6-yarns.Information about the γ-phase can be obtained from equatorial and meridional reflections. The expected relationship between the relevant peak areas was established. This reported evidence shows the physical validity of the parameters obtained using the Pearson VII model for the analytical description of x-ray reflections of nylon-6 yarns.
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  • 30
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1201-1209 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass-transition temperatures of a series of copolymers of ethyl acrylate and acrylic acid neutralized with various cations were investigated. It was found that a plot of Tg as a function of ion content, for every type of ion investigated here, gives an unusual sigmoidal curve, which can be correlated with the onset of the failure of time-temperature superposition in viscoelastic studies, as will be shown in a future publication. Also, all of the Tg versus concentration curves for the various counterions can be superposed if the plots are made against cq/a, where c is the metal acrylate content, q the cation charge, and a the distance between centers of charge. Furthermore, in one region of water content, a linear relation is obtained between the glass transition and the water content (in weight-%) independent of the ion concentration over wide ranges of ion content. Finally, above an ion concentration of 12 mole-%, the rate of change in Tg per water molecule per ion pair at constant ion content, (∂Tg/∂n)c is linear but with different slopes above and below two water molecules per ion pair.
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  • 31
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1087-1095 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The changes which take place on annealing rigid PVC in the vicinity of the glass transition have been followed by differential scanning calorimetry. The changes appear as an increase in the glass-transition temperature and a decrease in the enthalpy with time of annealing. For annealing at 75°C, the enthalpy after 50-100 hr approaches the value characteristic of the equilibrium liquid state. The results obtained for annealing at 65°C and 75°C are in accord with those expected for the relaxation of an amorphous material, and are at variance with those expected on the basis of crystallization taking place on annealing. The enthalpy relaxation process is characterized by a distribution of activation energies centered about 18.8 kcal mole-1, and seems to reflect a multiplicity of molecular processes.
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  • 32
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1149-1156 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt rheological behavior of an anionically polymerized styrene-butadiene-styrene (SBS) block copolymer sample (S: 7 × 103 and B: 43 × 103) was studied using a Weissenberg rheogoniometer. Highly non-Newtonian behavior, high viscosity and high elasticity, which are characteristics of ABA type block copolymers, were observed at 125°C, 140°C, and 150°C. The data at these temperatures superimposed well onto a master curve giving a constant flow activation energy. However, the data at 175°C indicated a marked change in the flow mechanism between 150°C and 175°C. At 175°C, the sample showed Newtonian behavior, negligible elasticity, and deviation from the master curve. These findings may be considered as an indication that the SBS block copolymer sample undergoes a structural change from a multiphase structure at low temperatures into a homogeneous structure at some temperature between 150°C and 175°C.
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  • 33
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1161-1167 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new crystalline form of isotactic poly(pentene-1) was obtained from dilute solution in amyl acetate. We have designated it as form III. The morphology and structure of isothermally crystallized samples were investigated by electron microscopy and electron and x-ray diffraction. This crystalline modification can be indexed on an orthorhombic unit cell (cell dimensions: a = 21.20 ± 0.05 Å, b = 11.48 ± 0.05 Å, c = 14.39 ± 0.05 Å (fiber axis) and probable space group P212121).
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1187-1199 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Glass-transition temperatures and phase separation have been studied in amorphous bisphenol-A polycarbonate plasticized with pentaerythritol tetranonanoate (PETN), trimellitic acid, tridecyloctyl ester (TMDO), and tritolyl phosphate. (TTP). Phase separations occur with partially compatible plasticizers like PETN or TMDO. With PETN, for compositions situated in the miscibility gap, the system is composed of a pure plasticizer phase and of a plasticized polymeric phase characterized by a transition temperature of 110°C. In the case of TMDO and additional phase separation occurs below 55°C and two plasticized polycarbonate phases are observed. In compositions falling in the region where the could point curve crosses the glass-transition diagram the phase separation may be delayed by quick cooling. TTP is completely compatible with polycarbonate and the variation of the glass-transition temperature follows a Gordon and Taylor equation.
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  • 35
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1235-1240 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An x-ray back-reflection rotating camera has been used to measure the lattice constant, thermal expansion, and compressibility in the polymer chain direction of a polydiacetylene, poly[bis(p-toluene sulfonate) of 2,4-hexadiyne 1,6-diol]. The thermal expansion coefficient of the polymer chain is small and positive (0.9 ± 0.2 × 10-6 °K-) at 300°K, but negative below about 70°K. Application of 3.43 kbar hydrostatic pressure at 299°K changed the unit cell dimension in the polymer chain direction by less than 10 ppm.
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  • 36
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1425-1431 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Persistence vectors a ≡ 〈r〉 are calculated for polypropylene, polystyrene, and poly(methyl methacrylate) chains as functions of chain length and stereochemical constitution. Differences between the progressions of a with chain length for these vinyl polymers are related to their conformational characteristics. The preferences of the syndiotactic chains for the tt dyad conformation are manifested most strikingly in the behavior of this vector.
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  • 37
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent-cast films of blends of poly(∊-caprolactone) (PCL) with poly(vinyl chloride) (PVC) were examined by low-angle x-ray scattering and by small-angle light scattering. X-ray scattering from crystalline compositions were analyzed using the Tsvankin-Buchanan technique and led to values of the repeat period of the lamellar structure and the thickness of the crystalline and amorphous layers. With increasing content of PVC, the amorphous layer thickness increased sufficiently to accommodate the PVC, leading to values of the linear crystallinity consistent with macroscopic measurements by density and DSC techniques up to about 50% PVC by weight. Above this concentration, the lamellar structure no longer appeared to be volume filling. At high concentration of PCL, the polymer consisted of volume-filling spherulites containing the lamellar substructure. Spherulite sizes were measured by light scattering and absolute light scattering intensities were consistent with calculations based upon the degree of crystallinity and anisotropy of the spherulites. Compositions containing more than 60% PVC were amorphous. Low-angle x-ray scattering was interpreted in terms of the Debye-Bueche theory which leads to values for a correlation distance lc and the mean-square electron density fluctuation 〈η2〉 (which was also obtained from the invariant). By the method of Porod, the correlation distances were resolved into persistence lengths within the two phases, which were determined as a function of composition. The fluctuation 〈η2〉 was analyzed in terms of a two-phase model to show that its value was somewhat larger than would be obtained if the phases were composed of the pure components. It was not possible to uniquely determine their compositions. The data were consistent with the existence of a transition zone of the order of 30 Å thick between phases.
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  • 38
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1485-1493 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The universal calibration for gel permeation chromatography (GPC) has been applied to amylose and dextrans. The molecular weight distribution of amylose has been measured starting from known data on dextrans. The agreement found between the molecular weight averages resulting from GPC and those obtained by other methods justifies the procedure followed. The GPC measurements were performed with dimethylsulfoxide as the elution solvent and deactivated silica gel (Porasil) as the column-filling material.
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  • 39
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1495-1512 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Unoriented T-die flat films of nylon 6 and PET films annealed at 90°C were stretched in water at 80°C. Amorphous PET films were stretched in water at 65-75°C. Changes in the light scattering patterns from these samples upon stretching were investigated. One of the observed LS patterns from the stretched samples is the Hv eight-leaf pattern consisting of four lobes and streaks. In the nylon 6 and heat-treated PET showing this pattern, spherulitic patterns can be seen in polarization microscopy. The microscopic spherulitic superstructure may possibly be the factor responsible for producing the lobe-and-streak pattern. On the other hand, many microscopic eight-leaf patterns can be observed in amorphous unannealed PET showing the lobe-and-streak pattern. These microscopic patterns are due to retardation at stress concentrations around impurities and nuclei. The superstructure giving these microscopic patterns must be the origin of the lobe-and-streak pattern from unannealed PET. Another scattering pattern, the Vv cruciform pattern, was observed in both stretched nylon 6 and unannealed PET. This pattern is due to an orientation change across the slip lines observed under a polarizing microscope. It is noted (1) that the appearance of the slip lines in PET coincides with the occurrence of oriented crystallization on stretching, (2) that the lobe-and-streak pattern from PET in which orientation crystallization has taken place is fairly stable to heat treatment and does not disappear until just before melting, and (3) that the superstructures produced at low stretching seem to be deformed on further stretching, in accordance with affine deformation theory.
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  • 40
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1567-1573 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An Interesting kinetic effect in the environmental stress cracking (E.S.C.) of polyethylene has been observed, in which the liquid viscosity plays an important role. E.S.C. of a low density, high melt index polyethylene due to silicone oils has been studied using constant load creep experiments. For relatively low stresses, it has been found that the time to fracture is independent of the viscosity of the silicone oil, all other factors being approximately equal. However, at high stresses, the time to fracture increases with increasing viscosity for a given stress. This effect has been shown to be due to the relative ease with which the liquid penetrates a growing crack and thus always be at the crack front. Times to fracture for viscous liquids at high stresses are longer since crack propagation continues partially with and partially without liquid contact, fracture rate being much slower when not in the presence of the liquid.
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  • 41
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1591-1599 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric β-relaxation in oriented poly(ethylene terephthalate) was investigated over wide ranges of frequency and temperature, with the electric field applied at inclinations of 0°, 45°, and 90° to the draw direction. Pronounced directional anisotropy is observed over the entire range of temperature and frequency. With the external field parallel to the draw direction the dielectric loss is considerably smaller than the value obtained with the field normal to the draw direction. The value obtained with the electric field at 45° to the draw direction is intermediate between the other two. On the other hand, the activation energy is largest for 0° inclination and smallest for 90° inclination. It is suggested that motions of the dipoles involve localized rocking of the molecular chain backbone, particularly when the external electric field is parallel to the chain direction.
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  • 42
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1659-1669 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical properties of cold-compacted films of polyethylene prepared by γ-ray-induced polymerization in bulk at 30°C are discussed in connection with the fine structure. The cold-compacted films show a broad α-relaxation at a lower temperature than do single-crystal mats or melt-crystallized polymer. From the effects of annealing and swelling by carbon tetrachloride on the relaxation, it is concluded that the α-relaxation, like the α-relaxation in the single-crystal mats, originates from molecular motions within lamellar crystals. This is consistent with the finding that these films are composed of stacked small irregular lamellar crystals. The γ-relaxation is also similar to that in crystal mats.
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  • 43
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1641-1658 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The drawing behavior of a series of linear polyethylene homopolymers with weight-average molecular weight (M̄w) ranging from 67,800 to ∼3,500,000 and variable distribution (M̄w/M̄n = 5.1-20.9) has been studied. Sheets were prepared by two distinct routes: either by quenching the molten polymer into cold water or by slow cooling below the crystallization temperature (∼120°C) followed by quenching into cold water.When the samples (2 cm long) were drawn in air at 75°C using a crosshead speed of 10 cm/min it was found that for low M̄w polymers the initial thermal treatment has a dramatic effect on the rate at which the local deformation proceeds in the necked region. At high M̄w such effects are negligible. An important result was that comparatively high draw ratios (λ 〉 17) and correspondingly high Young's moduli could be obtained for a polymer with M̄w as high as 312,000. It is shown how some of the structural features of the initial materials (mainly studied by optical microscopy, small-angle x-ray scattering and low-frequency laser Raman spectroscopy) can be interpreted in terms of the molecular weight and molecular weight distribution of the polymers. Although crystallization and morphology can be important at low M̄w, it suggested that the concept of a molecular network which embraces both crystalline and noncrystalline material is more helpful in understanding the drawing behavior over the whole range of molecular weights.
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  • 44
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1693-1700 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spin-lattice relaxation times (T1) for methyl, methylene, and methine carbons in an amorphous polypropylene have been measured as a function of temperature from 46 to 138°C. The carbons from isotactic sequences characteristically exhibited the longest T1's of those observed. The T1 differences increased with temperature with the largest difference occuring for methine carbons where a 32% difference was observed. Activation energies were determined for the motional processes affecting T1's for isotactic and syndiotactic sequences with essentially no dependence upon configuration noted.
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  • 45
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1903-1907 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 46
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1913-1916 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 47
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1921-1929 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In evaluating molecular orientation by dynamic infrared techniques, it is shown, subject to certain restrictions, that an extensional mechanism plays an important role in the measured orientation. Dichroic measurements can indicate a change in segmental orientation without any change occurring in the chain axis orientation. Extensional orientation was evaluated for a general helical molecule in terms of singular and coupled vibrational modes. Significant orientation changes can occur by the extensional mechanism, the sign and magnitude of which depend on the components of the transition moment vector.
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  • 48
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1801-1812 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is proposed for calculating the activation energy over the entire temperature range from relaxation measurements at two frequencies as a function of temperature by taking into account the entire experimental curve. The method is independent of the distribution of relaxation times, but assumes the validity of the time-temperature superposition principle.
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  • 49
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1871-1875 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The γ and δ relaxations of polystyrene (PS) are rendered more active dielectrically by sorbed oxygen. This effect, coupled with comparative work on molecularly similar systems has led to the assignment of the γ relaxation to a rotational libration of the phenyl ring in PS. Specific interactions of the pendant phenyl ring with molecular oxygen to induce off-axis dipole moments in the phenyl moiety is proposed. It is concluded that this interaction is strong enough to influence the dielectric relaxation strength of other relaxations in PS. It is further concluded that because of the interactions occuring in aromatic polymers containing sorbed oxygen, care must be taken to exclude oxygen or to vary its content, in order that intrinsic motions in the polymer system can be studied.
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  • 50
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1909-1912 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 51
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1917-1919 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 52
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2105-2108 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 53
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2109-2112 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 54
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2119-2128 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene networks prepared by anionic polymerization have been characterized by small-angle neutron scattering. Two kinds of systems have been examined:(A) networks with labelled branch points allowing characterization of the spatial distribution of crosslinking points; (B) networks containing a low proportion of chains labelled with perdeuterated polystyrene in order to characterize the conformation of individual elastic chains of the polymeric network. The dependence of the results on swelling and uniaxial extension is discussed.
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  • 55
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2129-2136 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation of birefringence and stress in simple extension has been studied for polyisobutylene at -26.0°C and 25.0°C for extension ratios ranging from about 1.2 to 2.0. The dependence of both the stress and birefringence on the extension ratio, for a given time, is well described by equations of the Mooney-Rivlin form. The Mooney-Rivlin treatment of the birefringence experiments was found to reinforce but not add to information available from the stress-relaxation experiments alone. At 25.0°C, the stress-optical coefficient is found to be stress dependent. Possible explanations of this behavior are discussed. An experiment is also reported in which the birefringence is observed under zero stress immediately after cutting a strained sample. The zero stress birefringence is believed to be due to regions of stress-induced crystallization taking a finite time to melt after the stress is removed.
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  • 56
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2195-2209 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lateral swelling, changes in length and tensile stress-strain curve of reconstituted collagen hollow fibers, crosslinked with uv irradiation, were measured as a function of the pH and ionic strength of their aqueous environment. From pH 5 to pH 10 the lateral swelling and length are constant; at lower and higher pH the lateral swelling increases rapidly while the fiber shrinks in length. Corresponding to these changes, a pronounced toe develops in the stress-strain curve and extends to a higher strain in more acid (or basic) media. This toe is attributed to the straightening of a microcrimp in the collagen fibrils; the microcrimp is accentuated by the repulsion between the charged fibrils in acid or basic media. Direct small-angle x-ray evidence of these microcrimp structure changes at low pH is presented. Increasing the ionic strength of an acid solution by adding NaCl decreases the lateral swelling, increases the length, and decreases the extent of the toe on the stress-strain curve. These changes result from an increased screening of the charge on neighboring fibrils at higher ionic strengths thus decreasing the repulsion between fibrils and the resulting microcrimp. Although the zigzag elastica model of the crimp developed by Diamant et al. [Proc. Roy. Soc., Ser. B, 180, 293 (1972)] provides a good empirical fit to the stress-strain data, it is shown to be inappropriate where the crimp results from repulsive forces between fibrils. A new model taking these forces into account is developed and is shown to be in reasonable agreement with the experimental results.
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  • 57
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2231-2240 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mean-square dipole moments of poly(ethylene oxide) and poly(hexamethylene oxide) chains have been determined from dielectric constant measurements on dilute solutions of the polymers in benzene. The values obtained are in good agreement with those predccted using the rotational isomeric state models for these chains. In addition, the unperturbed dimensions of poly(hexamethylene oxide) have been calculated as a function of molecular weight, using the isomeric state theory.
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  • 58
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2253-2257 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of phase transformation are treated for heterogeneous nucleation, where all nuclei are simultaneously initiated, and where initiation follows first-order kinetcs. The phase transformation curves are sigmoid. For simultaneous initiation in two dimensions, a(t)/(1 - a(t)) ∝ t2. For first-order initiation, we have, approximately, a(t)/(1 - a(t)) ∝ t2.85, and v(t)/(1 - v(t)) ∝ t3.74.
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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2241-2251 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cloud-point curves have been determined for aqueous solutions of poly(ethylene oxide) (PEO) at several concentrations for a variety of inorganic salts (sulfates, carbonates, nitrates, and chlorides). From these, theta conditions have been determined. The resulting dependences of the critical temperature θ (mostly between 300 and 360°K) on the molar concentrations (or ionic strengths) of the salts in solution cannot wholly be summarized in sequences of ion effects. The major findings are that sulfates and carbonates are much more effective in reducing θ than the chlorides and nitrates at the same concentrations. The trends found depend on salt concentration, i.e., certain plots of the data cross over, but they broadly agree with those found for comparable systems by other workers. Exceptional are the chlorides of Group II and LiCl which show minima when θ is plotted against molar salt concentration. While interpretations based on solvent structure-breaking are not adequate, there are similarities in behavior with the structure-breaking attributes of the ions based on independent studies (infrared). The results are briefly discussed in terms of current postulates: a more detailed discussion will accompany further experimental studies on these systems.
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  • 60
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2273-2284 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Six 6,10-ionenes with different counterions were prepared by ion exchange reactions in aqueous solutions. The counterions were Br, I, CIO4, BF4, SCN, and B(C6H5)4. The dynamic mechanical properties of these polymers were investigated by use of a torsional braid analyser. Three relaxations α (25-140°C), β (-30-0°C), and γ (-140-120°C) were observed at the frequencies of 0.3-0.8 Hz. The temperature of the α and β relaxations were largely dependent on the size of counterions, but those of the γ relaxations had little variation. The effects of electrostatic forces in the polymers on each relaxation was discussed. The influence of absorbed water on the α, β, and γ relaxations was examined. The absorbed water in the polymers greatly depressed the temperature of the α relaxations and this phenomenon was interpreted to be the result of the specific hydration on ionic portions.
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  • 61
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2291-2311 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle and wide-angle x-ray scattering measurements, using a position-sensitive detector, were made during melt-crystallization of linear polyethylenes and PEO-PS-PEO triblock copolymer. The scattering measurements indicated that the triblock copolymer grew by the enlargement of regions in which lamellae are regularly stacked. During primary crystallization at higher temperatures similar behavior is observed in two linear polyethylenes. At lower temperatures, changes in the shape of small-angle scattering curves during the primary stage of crystallization indicate that amorphous gaps within the lamellar stacking become filled in. During secondary crystallization at higher temperatures new crystallites appear to grow between those formed in the primary stage. Concurrent decrease of the overall scattered intensity leads to the conclusion that secondary crystallization has two components: crystallization of new lamellae behind the spherulite growth front and the thickening of existing lamellae.
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  • 62
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1241-1255 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fibers were drawn from polymers of octadecyl acrylate, octadecyl methacrylate, N-octadecylacrylamide, and a series of N-substituted acrylamides with a second amide group in the side chain as well as from copolymers of octadecyl and methyl esters of acrylic and methacrylic acid. Wide-angle and small-angle x-ray diffraction patterns were recorded for these materials. The interpretation of the characteristic difference between the behavior of the polycrylates and polymethacrylates, as proposed by Platé and his collaborators, is found to be inconsistent with a number of features of the experimental evidence. In the case of poly(octadecyl methacrylate) the data allow the estimation of two parameters of the electron density distribution in the side-chain crystallites. With polyacrylamide derivatives, a second amide group in the side chain is found to destabilize the side chain crystallites. The bahavior of the copolymers is very complex and exhibits, in one case, evidence for a long periodicity parallel to the fiber axis.
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  • 63
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1287-1295 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrophobic-hydrophilic block copolymers were prepared by “living” anionic polymerization. They consist of polystyrene and poly(ethylene oxide) blocks, and are soluble in water. Their interfacial properties were investigated, employing aqueous solutions. The block copolymers lowered the surface tension of water in analogy with the low molecular weight surfactants such as sodium lauryl sulfate and heptaethylene oxide n-dodecyl ether. Their aqueous solutions exhibited solubilization properties differing from those of polyethylene glycol. Therefore, it is thought that the polystyrene blocks produce solubilization phenomena. In samples of the same styrene content, the precipitation temperature of a high molecular weight copolymer in water was lower than that of a low molecular weight copolymer at the same concentration in the same solvent. The surface tension and precipitation temperature of aqueous solutions seem to be influenced by molecular weight and composition.
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  • 64
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1317-1324 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A weak acid gel (carboxylmethyldextran) was titrated with sodium hydroxide while equilibrated with a solution sodium poly(vinyl sulfate), a salt of a strong acid polyelectrolyte.It was found that the quantity \documentclass{article}\pagestyle{empty}\begin{document}$$ S = {\rm pH} - {\rm pNa} + \log (V/V_0) $$\end{document} in which V/V0 is the volume of gel relative to its volume in acid form in pure water, is independent of the concentration Cp of the polyelectrolyte solution and of the relative volume of gel.The relation \documentclass{article}\pagestyle{empty}\begin{document}$$ S - \log \left({\frac{{\alpha ^2}}{{1 - \alpha}}} \right) = {\rm pK'} + \log \gamma _{{\rm Na}}^{\rm g} + \log (v/V_0) $$\end{document} where α is the degree of ionization, pK′ is the apparent pK of the gel, γnAG is the activity coefficient of the counterion in the gel phase, and v is the number of ionizable groups, is found to be constant for all values of Cp and for 0.1 〈 α 〈 0.9. These results can be extended to highly crosslinked ionexchange resins.
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  • 65
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1891-1901 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nonisothermal creep experiment has been analyzed to ascertain its suitability for determining the temperature dependence of low activation energy viscoelastic processes in elastomers far above Tg. The nonisothermal method was employed to determine the activation energy for creep near 35°C in a lightly crosslinked cis-1,4 polybutadiene elastomer at small strains within the linear viscoelastic region, and at various large deformations up to rupture. The observed activation energy was essentially independent of the level of strain, and the value of ΔHa (∼11 kcal/mole) determined via the nonisothermal creep method was in good agreement with the result (∼12 kcal/mole) obtained via time-temperature superposition of isothermal linear viscoelastic creep data. The nonisothermal data allowed for an estimate of the volume of the “flow unit” associated with the controlling viscoelastic creep mechanism, attributed here to slippage of entanglements within the lightly crosslinked network.
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  • 66
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1877-1890 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation and Brillouin scattering are jointly used in studying molecular relaxation in poly(propylene oxide) (PPO) and its solutions in methylcyclohexane. The dielectric method was applied to the more concentrated (100%, 80%, 60%, by volume) solutions over a wide temperature and frequency range (30 Hz to 8 GHz) in order that the variation in activation energy characteristic of a glass-forming substance could be delineated. The present work extends previous work on the undiluted polymer to higher frequencies so that range of 12 decades in the dielectric loss maximum fmax as a function of temperature is now available. The “Antoine” equation is found to represent the behavior of log fmax, of the bulk concentrated solutions very well. The more dilute (40%, 20%) solutions were studied only in the high-frequency (GHz) region since phase separation occurred at low temperatures. Both the temperature and dilution effects were interpreted in terms of free-volume theory. Brillouin scattering spectra were obtained at several scattering angles and a wide range of temperatures. A maximum in the curve of hypersonic attenuation versus temperature was observed in each polymer solution. The attenuation maximum shifts toward lower temperature upon dilution, in agreement with the dielectric relaxation result. The Brillouin scattering follows different activation parameters and evidences a more rapid process than does the dielectric relaxation. It is speculated that it monitors a secondary or subglass relaxation, due perhaps, to damped torsional oscillations.
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  • 67
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 165-171 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of chloroprene-methyl methacrylate copolymers in the presence of Lewis acids (Et1.5AlCl1.5) in hydrocarbon solvent and the effect of Lewis acids concentration on copolymer composition are described. 13C NMR spectra were obtained on these copolymers. In samples of high MMA content, tactic placements of MMA were observed as well as several different kinds of sequences for chloroprene and MMA. In samples of low MMA content, no tactic placements of MMA were found but several different kinds of chloroprene sequences were observed. From the analysis of the 13C NMR spectra of the different copolymers examined, it is apparent that all the various kinds of chloroprene sequences in these copolymers can be determined.
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  • 68
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 187-210 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been made of the crosslinking of linear polyethylene in solution. Networks containing a low number of trapped entanglements and elastically ineffective chain ends were prepared by crosslinking high molecular weight linear polyethylene in 1,2,4-trichlorobenzene solutions with dicumyl peroxide at 120°C. No syneresis was observed during crosslinking except at high peroxide concentrations. The networks were characterized by swelling measurements, infrared spectroscopy, and differential scanning calorimetry. The crosslinking efficiency, calculated from swelling, was found to be proportional to the square of the polymer volume fraction. The proportionality constant was 0.8, indicating close to unit efficiency for undiluted polymer.Chemical modification of the polyethylene chains by attachment of peroxide and solvent fragments was of the order of one foreign unit per elastically active network chain, depending on peroxide and polymer concentration. Sol-gel analysis indicated that no chain scission occurred. These results are shown to be consistent with a “cage” mechanism for crosslinking. The possible topological consequence of this mechanism, preferential crosslinking of entanglements, is discussed. The concentration of trapped entanglements was also found to be proportional to the square of the polymer volume fraction. The proportionality constant corresponds to a molecular weight between entanglements of 4000 for the undiluted polymer, which is close to the value of 4200 found for networks prepared from the undiluted polymer. Since the results obtained are based mainly on the use of the swelling equation, different aspects of the applicability of this equation for the evaluation of the crosslinking process are discussed. As regards the reference dimensions, which should be known for a quantitative application of the elastic theory, the results strongly support the use of the dimensions of the network chains after completion of crosslinking.
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  • 69
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 251-262 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isolated spherulites of poly(methyl D-glutamate) (PMDG) were nucleated in bromoform. The morphology of these spherulites was investigated by SEM and photographic small-angle light scattering (SALS). From the SALS patterns, the development and growth of the spherulites could be noted. Films of PMDG cast from bromoform solution were found to be partially spherulitic. The mechanical properties of these films, prepared by different procedures, were compared with the general behavior of PMDG films cast from chloroform, the latter of which does not contain spherulitic texture.
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  • 70
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 299-308 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data are presented to show that two correlations of viscosity-concentration data are useful representations for data over wide ranges of molecular weight and up to at least moderately high concentrations for both good and fair solvents. Low molecular weight polymer solutions (below the critical entanglement molecular weight Mc) generally have higher viscosities than predicted by the correlations.One correlation is ηsp/c[η] versus k′[η], where ηsp is specific viscosity, c is polymer concentration, [η] is intrinsic viscosity, and k′ is the Huggins constant. A standard curve for good solvent systems has been defined up to k′[η]c ≍ 3. It can also be used for fair solvents up to k′[η]c ≍ 1.25· low estimates are obtained at higher values.A simpler and more useful correlation is ηR versus c[η], where ηR is relative viscosity. Fair solvent viscosities can be predicted from the good solvent curve up to c[η] ≍ 3, above which estimates are low. Poor solvent data can also be correlated as ηR versus c[η] for molecular weights below 1 to 2 × 105.
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  • 71
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 317-322 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray line broadening measurements were used to determine the apparent “mosaic block” sizes of randomly oriented polyethylene and polyoxymethylene single crystals. Both dried-down and uncollapsed crystals were examined. PE lamellae were grown at 80, 85, and 90°C by isothermal crystallization from a 0.1% solution in xylene. POM crystals were grown at 125°C by self seeding from an 0.05% solution of the polymer in o-dichlorobenzene. A given preparation was split into two parts. One part was dried down in the usual manner, the other was exchanged to paraffin oil and the crystals never permitted to dry down. Previously reported studies used dried-down crystals and gave crystallite sizes of approximately 300 Å. More recently, using electron microscopy, it has been postulated that PE single crystals are free of “mosaic block” over regions of several thousand angstroms. It is evident from this present study that crystallite sizes in uncollapsed lamellae are significantly larger than those observed for the same crystals dried down. In the case of uncollapsed lamellae, one can explain the observed crystallite sizes solely on the basis of chain obliquity rather than by invoking the “mosaic block” model. It has also been determined that there is an upper limit to the crystallite sizes that can be observed in PE and POM crystals using wide-angle x-ray techniques. This limit may account for discrepancies between x-ray and electron diffraction.
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  • 72
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 323-342 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology and thermal behavior of trans-1,4-polybutadiene single crystals prepared from dilute solutions in n-heptane have been investigated by electron microscopy, wide-angle and low-angle x-ray diffraction, and differential scanning calorimetry. The thickness of the single crystals of trans-1,4-PBD is much greater, for the same undercooling, than that of other linear polymers. From the calorimetric study, convincing evidence of the presence, in the single crystals, of crystalline blocks of form 1 with two different thermodynamic stabilities is obtained and the relative amounts are calculated. From thermodynamic considerations we find a value of 75°C for the equilibrium transition temperature between forms 1 and 2, 139°C for the equilibrium melting temperature of form 2, and 31.2 erg/cm2 for the fold-surface free energy of modification 2.
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  • 73
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 343-352 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complete and partial alcoholyses of ethylene-vinyl acetate (E-VA) copolymers yield ethylene-vinyl alcohol (E-VOH) copolymers and ethylene-vinyl acetate-vinyl alcohol (E-VA-VOH) terpolymers, respectively. From the 220-MHz proton NMR spectra of E-VOH copolymers the stereoregular and chemical sequence distributions of the comonomers can be readily determined. Partially hydrolyzed E-VA polymers were acetylated with perdeuterated acetic anhydride. The monomer distributions in the terpolymers were then quantitatively determined by examining the proton spectra of the derived products. It was found that alcoholysis of E-VA polymers occurs preferentially at VA units which have neighboring VA groups.
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 353-365 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle x-ray scattering (SAXS) from quenched and annealed rigid polyvinyl chloride (PVC) has been measured using a Bonse-Hart system. After correcting for absorption, background, and beam divergence, the scattering has been placed on an absolute basis using a standard silica suspension as a reference. The scattering from annealed (6 days at 75°C) and unannealed PVC was identical within experimental error, varying with scattering angle in a manner similar to the SAXS from other amorphous polymers. The intensity decreases rapidly with increasing scattering angle over the ranges from 20 sec to 20 min. Beyond 20 min the intensity is fairly constant, decreasing only slightly with increasing angle. At the largest angles of measurement (in the range of 120 min), the measured intensity is close to the value calculated for thermal density fluctuations frozen-in at the glass transition.The angular variation of intensity is well described by the scattering from heterogeneities of various sizes and concentrations superimposed on the scattering from thermal density fluctuations. These heterogeneities range in radius from 50 to 4500 Å and, assuming the crystalline excess density, the total concentration of heterogeneities is less than 0.5%. The mean-square fluctuation in density, determined from the measured intensity invariant, is also consistent with such a distribution of heterogeneities.The present SAXS results on rigid PVC are inconsistent with the presence of nodular features as representative of the bulk polymer. Rather, it is suggested that they are associated with surface effects. It is further suggested that previously indicated volume fractions of crystallinity in rigid PVC (generally in the range of 5-12%) are incorrect, and that the model of a three-dimensional network of crystallites used to explain the rheological behavior of this material should be re-examined.
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  • 75
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 427-435 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of poly(m-phenyulene isophthalamide) was determined by x-ray analysis. The triclinic cell, with a = 5.27 Å, b = 5.25 Å, c (fiber axis) = 11.3 Å, α = 111.5°, β = 111.4° and γ = 88.0° and space group P1, contains one monomeric unit. The crystal density is 1.47 g/cc. The molecules in the crystal are contracted by 1 Å per monomeric unit from the fully extended conformation, and the planes of the benzene rings and adjacent amide groups make angles of about 30°. The crystal is composed of molecular chains connected by N—H···O hydrogen bonds along the a and b axes forming a “jungle gym” network structure. The low tensile modulus of this polymer as compared with that of poly(p-phenylene terephthalamide) is attributed to the contracted molecular conformation.
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  • 76
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 521-529 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectroscopy has been used to analyze the characteristics of the crystal-crystal phase transition of trans-1,4-polybutadiene. The low- and high-temperature structures were found to coexist at the transition. The Raman spectra obtained at high temperature can be understood on the basis of the change in chain conformation associated with the phase transition.
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  • 77
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation of stress and birefringence in simple extension has been studied for two samples of 1,2-polybutadiene with 95% and 88% vinyl content and weight-average molecular weight 1.9 and 2.9 × 105, respectively. The extension ratio, λ, ranged from 1.14 to 2.08, temperatures from 0 to 15°C, and times, reduced to 0°C, up to 3 × 105 sec. The stress-optical coefficient C was negative and positive, respectively, for the two samples, the difference being attributable to opposite signs and very different magnitudes of the contributions of the 1,2 and 1,4 moieties to the birefringence. For each polymer, C was independent of time but increased (algebraically) with temperature. For one polymer a very minor dependence of C on λ was observed. At any instant of time, the dependence of both stress and birefringence on λ could be described by equations of the Mooney-Rivlin form with coefficients C1,C2 and B1,B2, respectively. At short times the contributions of the C1 and C2 terms to the stress and of the B1 and B2 terms to the birefringence are roughly equal. With increasing time, C1 and B1 decrease gradually while C2 and B2 remain constant over several decades in time. Finally, C2 and B2 decrease rather rapidly. A tentative interpretation of these phenomena in terms of motions of entanglements is given.
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  • 78
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 759-768 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data on styrene-acrylonitrile (St-AN), and styrene-methyl methacrylate (St-MMA) copolymers reported in Part I of this series are tested by “two-parameter” theoretical relations. The Fox-Flory (F-F) parameter K is estimated using the F-F, Stockmayer-Fixman (S-F), and Inagaki-Ptitsyn (I-P) equations. In general, the K values obtained by the F-F equation are low for the three St-AN copolymer samples in the systems studied while the values obtained from S-F and I-P equations agree within the limits of experimental error. Values of K obtained from Kurata-Stockmayer (K-S) equation for sample SA1 agree with values obtained by the S-F and I-P equations. The specific solvent effect on the K values is discussed. Values of the unperturbed dimension r̄02/M̄w, calculated from the K values estimated from the S-F equation and from the homopolymer data are compared. Except in one case, the calculated r̄02/M̄w values from homopolymer data are low in comparison with the values obtained from experimental data, which shows that the presence of the repulsive interactions between unlike monomer units brings about an expansion of copolymer molecule. The effect of composition on the steric factor σ values is discussed. The long-range interaction parameter B, the excess interaction parameters ΔBAB, and χAB are calculated. The effects of composition and solvent on these parameters are discussed.
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  • 79
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 821-831 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The possible explanations for the temperature-induced reversible changes in long spacing in polymers are reviewed. The observation of particularly large changes in certain irradiated samples of oriented low-density polyethylene is reported. By combining these results with those obtained by DSC and other means it is concluded that the spacing changes are caused by partial melting of small lamellae within the lamellar stacks which alters the mean periodicity. The requirement of an irregular lattice explains why the effect is observed primarily in bulk samples and especially in materials which contain intrinsic irregularities.
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  • 80
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 861-867 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique is described which enabled exceptionally thin sections of rubbery material to be cut for electron microscopy, and applied to samples of polystyrene-polybutadiene-polystyrene (SBS) copolymers which contain the segregated S phase in the form of cylinders arranged in a regular hexagonal macrolattice throughout the macroscopic specimen, with center to center distance of 300 Å. The technique consisted of sectioning the material hardened by a combination of osmic acid treatment and cooling with liquid air. By this method longitudinal sections containing single layer S rods could be obtained as verified by appropriate tilting tests. Such sections enabled the viewing of single cylinders without overlap which in turn enables the study of the structure of individual cylinders and the effect of various treatments on this structure. Examples quoted include the yielding or breaking of individual cylinders on longitudinal deformation of the macroscopic sample relating to our mechanical studies to be reported elsewhere. The technique also enabled sectioning in the swollen state of samples which are not sectionable other wise and this leads to the recognition of new structures and results in an overall improvement of image quality even when the thinness itself is not the prime requirement.
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  • 81
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 879-895 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Metal-insulator-semiconductor (MIS) techniques were used to show that 86-210 nm thick plasma-polymerized tetrafluoroethylene films on silicon stored only negative charge (electron acceptors). This property persisted at a reduced level when a 7 nm thick inner layer of hydrolyzed γ-aminopropyltriethoxysilane was combined with an outer layer of plasma-polymerized tetrafluoroethylene. The dispersion force contribution to the surface energy, γds, for the fluorocarbon films was found to be 6 mJ/m2 (erg/cm2) which is comparable with the lowest values found in the literature. X-ray photoelectron spectroscopy (XPS) revealed a substantial content of —CF3 groups in the fluorocarbon films. This finding coupled with the reported effects of noncrystallinity, crosslinking, and branching on the surface energies of fluorocarbon systems were used to explain the low surface energy and electrophilicity of the plasma-deposited poly(tetrafluoroethylene)s.
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  • 82
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 913-920 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple treatment based on continuum mechanics shows that weak interlamellar forces in crystalline n-alkanes should result in a characteristic upward shift of the frequencies of the longitudinal acoustical (LA) modes, which is independent of the chain length and decreases inversely with the mode order. A raman spectroscopic determination of the LA mode frequencies of a series of different n-alkanes confirms the theoretical conclusion and permits a derivation of a force constant characteristic of the interlamellar forces. The discussion results in a new formula valid for the LA mode frequencies of the orthorhombic n-alkanes in the acoustical limit and yields a new determination of the limiting elastic modulus Ec of crystalline polyethylene. The value obtained, Ec = 2.9 × 1012 dyne/cm2, is markedly smaller than the value derived by Schaufele and Shimanouchi neglecting the influence of the interlamellar forces on the LA mode frequencies.
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  • 83
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 959-961 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 84
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1097-1109 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectra of polarized light scattered from model networks of polystyrene swollen by benzene have been measured by optical mixing spectroscopy. Various series of networks of different functionalities and different lengths of the elastic chain elements have been investigated. A theoretical expression for the characteristic time constant of fluctuations has been derived from rubber elasticity theory. An analysis of the experimental results within the framework of this theory allows determination of the frictional constants of the gels.
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  • 85
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1451-1459 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface tension γ of four copolymer latices, of their respective serums, and of aqueous solutions of dispersant alone were measured at various dilutions. By extrapolating the surface excess of dispersant (calculated by the Gibbs adsorption equation) both at the aqueous solution surface and at the serum surfaces to 1/c = 0 (c being the bulk concentration of dispersant) the same limiting site area Alim per adsorbed molecule was determined. Amounts of dispersant adsorbed by copolymer particles at various dilutions were determined from differences between the known total concentrations of the dispersant in latex and in serum at the same γ. These values were then extrapolated to the maximum adsorption at 1/c = 0 in latex. The surface area of copolymer particles was determined therefrom by using Alim. The average particle radius calculated this way agrees reasonably well with electron microscope measurements. Thus it appears that the method for determining latex particle surface area by surfactant titration may be calibrated by means of the Gibbs adsorption equation, provided one uses Alim and not the site area at the critical micelle concentration of dispersant.
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  • 86
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1629-1639 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intrinsic viscosities have been measured at 25° on five ethylene-propylene copolymer samples ranging in composition from 33 to 75 mole-% ethylene. The solvents used were n-C8 and n-C16 linear alkanes and two branched alkanes, 2,2,4-trimethylpentane and 2,2,4,4,6,8,8-heptamethylnonane (br-C16). This choice was based on the supposition that the branched solvent would prefer the propylene segments and the linear solvent the ethylene segments, due to similarity in shape and possibly in orientational order. It was found that [η]n - [η]br ≡ Δ[η] is indeed negative for propylene-rich copolymers, zero for a 56% ethylene copolymer, and positive for ethylene-rich copolymers. The Stockmayer-Fixman relation was used to obtain from Δ[η] a molecular-weight independent function of composition. The quantities (Δ[η]/[η])(1 + aM-1/2) and Δ[η]/M are linear with the mole percent ethylene in the range investigated with 200 ≤ a ≤ 2000. The possibility of using these results for composition determination in ethylene-propylene copolymers is discussed. Intrinsic viscosities in the same solvents are reported for two samples of a terpolymer with ethylidene norbornene.
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  • 87
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1717-1720 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 88
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of the shear stress at the start of shear flow at constant rate of shear κ was measured for polystyrene solutions in diethyl phthalate with a cone-and-plate rheometer. Ranges of molecular weight M and concentration c were 3.10 × 106-7.62 × 106 and 0.112-0.329 g/cm3, respectively. The shear stress as a function of time t exhibited a marked maximum at large κ when either M or c was relatively low. When M and c were high, the maximum was broad and low. In a few extreme cases no maximum was observed in the range of κ studied. The constitutive model of Bernstein, Kearsley, and Zapas could describe approximately the shear stresses at a sudden start and on cessation of steady shear flow with a memory function evaluated from the strain-dependent relaxation modulus. The strain dependence of the memory function for solutions of low M or c was approximately expressed as exp{-α|s|} where α is a constant (ca. 0.37) and |s| is the absolute value of shear strain. When M and c were high, the strain dependence was found to be more diffuse and to require several terms if approximated by exponential functions of |s|. The Lodge model based on a strain-rate dependent relaxation spectrum was not able to describe the strain-dependent relaxation modulus as well as the interrelation between shear stresses at a sudden start and a cessation of steady shear flow.
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  • 89
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1729-1730 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 90
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1755-1767 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low dielectric loss polyethylenes have been produced by γ-radiation polymerization of oxygen-free ethylene monomers. Dielectric measurements were made at 500 MHz and 20°C. The lowest dielectric loss tangent of the polyethylene was 3.3 × 10-5. Polar groups contributing to the dielectric loss have been found to be carbonyl groups, terminal vinyl groups, methyl groups, and hydroxyl groups contained in the polyethylene. The contribution of each group to the loss tangent has been calculated from a comparison of the variation of the loss tangent with the content of each group as determined by infrared analysis. It has been found that the reduction of the loss tangent is mainly due to the decrease in the concentrations of the carbonyl groups and the terminal vinyl groups and that the presence of a considerable amount of the hydroxyl groups prevents a further reduction of the loss in the polyethylenes. The results obtained from the analysis of the radiation-polymerized polyethylenes were applied to commercially available polyethylenes.
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  • 91
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1789-1800 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the temperature dependence of integrated intensities and from line widths in high-resolution 1H-NMR spectra, the relaxation times T1 and T2 of protons in CH2 and CH3 groups of polyisobutylene in CCl4 solution have been determined. Although the relaxation time T1 of methylene protons is determined mainly by intragroup interactions, intergroup interactions of two methyl groups from each two consecutive monomer units were found to contribute considerably to T1 of methyl protons. The Structure and mobility of polyisobutylene (PIB) molecules in solution is discussed on the basis of the relaxation time data.
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  • 92
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1839-1854 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly porous interpolymer ion-exchange membranes have been prepared from poly(styrene sulfonic acid), PSSA and poly(vinylidene fluoride) PVdF using a casting solvent of dimethylformamide and hexamethylphosphoramide. The membranes have been characterized by their water content, concentration potential, ionic conductivity, and their hydraulic permeability. An estimation of the porosity of the membranes has been made from the relative conductance of the potassium and the tetrabutylammonium ions in the film. This porosity has been compared with that derived from a consideration of the water flux through a Poiseuille-type pore.
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  • 93
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1725-1727 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 94
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1743-1753 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The azimuthal angular dependence of the depolarized component of the light scattered from spherulitic materials is derived by an algebraic method that avoids the difficult angular integrations of the usual approach. The result appears as a sum of products of two factors, a molecular factor, that depends only on the structure and the scattering angle θ, and a geometrical factor that depends only on the azimuthal angle φ and the scattering angle θ. The molecular factors are evaluated for models of spherulitic structure that assume a constant tilt of the optical polarizability tensor. The radial distribution, in principle, is arbitrary, and an evaluation for the layered spherulite is made. If the tilt angle is ω when the azimuthal patterns depend only on a linear combination of P2(cos ω) and P4(cos ω), where Pn(x) is the Legendre polynomial of order n. In our theory the VH scattering pattern is a four-leaf clover whose axes are restricted by the theory to be at either 0 or 45° to the polarization directions.
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  • 95
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1943-1952 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The incompatibility of polystyrene (PS) and polyisobutylene (PIB) in toluene is characterized by binodals obtained from phase separation and spinodals obtained from light scattering at zero scattering angle. From these the interaction parameter χ23, between unlike polymer segments was calculated. It appears to be dependent on molecular weight and composition. The nature of χ23, especially its low value, is discussed.
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  • 96
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1967-1977 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The angular dependence of light scattering from the homogeneous ternary system polystyrene + polyisobutylene + toluene was measured at a fixed (critical) concentration as a function of temperature. On approaching the critical temperature the scattering becomes very large and strongly angle-dependent. The experiments show that the interaction range rG is of the same order of magnitude as the molecular radius of gyration of the polymer, but cannot be set equal to it as in the case of a binary system of one polymer in a single solvent. The temperature dependence of the various interaction parameters does not depend on the molecular weights of the polymers.
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  • 97
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1931-1941 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An optical model of a system in which both polymer segments and solvent molecules are described as point dipoles has been used to calculate the intensity of light depolarized in scattering. The final expression consists of six terms, the physical meaning of which is briefly discussed. An approximation procedure has been worked out for the calculation of two interaction terms due to deviations of the local field in solution from the Lorentz-Lorenz field; the terms have been calculated for simple models of flexible and rigid molecules. Their dependence on molecular weight appears to be approximately the same as the intrinsic anisotropy of the polymer molecule; their contribution is nonzero even for a solvent isorefractive with the polymer.
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  • 98
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1953-1965 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering experiments are described on the system polystyrene (PS) + polyisobutylene (PIB) + toluene at constant temperature. At a fixed concentration of the nearly “invisible” PIB the light scattering at various angles was measured as a function of varying PS concentration up to the region of incompatibility. For interpretation of the results use is made of an extension of the classical fluctuation theory for multicomponent systems to finite scattering angles. The experimental data can be described qualitatively with this theory. Addition of a second polymer has little influence on the size of the other polymer. The variation of the light scattering with the wavelength can be explained in terms of the (negative) adsorption of one polymer by the other.
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  • 99
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2011-2017 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependencies of dynamic mechanical properties have been determined with a torsional pendulum for copolymers of ∊-caprolactone and γ-(tert-butyl)-∊-caprolactone over the entire composition range. Copolymers containing at least 25 mol % (33 wt %) of γ-(tert-butyl)-∊-caprolactone units are amorphous in nature. The experimentally obtained glass transition temperatures of the copolymers and poly(γ-(tert-butyl)-∊-caprolactone) were used to calculate the glass transition temperature of amorphous of poly(∊-caprolactone) according to the Fox relation. This value of -70°C is in excellent agreement with values obtained from similar calculations based on compatible blends of poly(∊-caprolactone) with other homopolymers.
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  • 100
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1337-1349 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Statistical mechanical averages of vectors and tensors characterizing the spatial configurations of polyoxymethylene (POM) and polyoxyethylene (POE) chains, i.e., the chain vector r connecting the ends of the chain and the tensors formed from this vector, are evaluated in internal reference frames attached to the first two bonds of each chain as functions of its length. Convergences of the persistence vectors a ≡ 〈r〉 with chain length to their limits a∞ are delineated. For POE, the orientation of a∞ with respect to the X1 axes (the direction of the first bond) depends markedly on the choice of the initial bond and hence also on the internal frame of reference. Cartesian tensors up to fourth rank formed from the displacement vector ρ = r - a are evaluated for n = 4-1922 bonds for POM and n = 3-300 bonds for POE. The second moment tensor 〈ρρT〉 calculated for POM is nearly cylindrically symmetric about the axis perpendicular to the plane of the first two bonds. Corresponding symmetry is absent in POE. Correlation with the freely jointed chain is investigated for the components of the tensors of fourth rank formed from the reduced vector \documentclass{article}\pagestyle{empty}\begin{document} $\tilde \rho = \left\langle {\rho \rho ^{\rm T} } \right\rangle ^{ - 1/2} \rho $\end{document}. Use of the equivalent chain model for this purpose is validated for POE but not for POM, even at n = 2000 bonds. At the limit 1/n = 0, the parameter m, representing the number of bonds of the real chain equivalent to one of the model, is estimated to be ca. 31 for POM. For POE a value of m = 10.3 ± 1.3 holds for n 〉 20 for all components. Results are compared with those calculated previously for polymethylene, poly(dimethylsiloxane) and polypeptides. The fact that values of m derived by analysis of moments are larger than those obtained in the usual manner by fitting the model chain to 〈r2〉0 and rmax for the real chain demonstrates the inadequacy of artificial models for the representation of the real chain.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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