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  • 1980-1984  (6,720)
  • 1965-1969  (3,364)
  • Physics  (4,506)
  • Chemical Engineering  (4,044)
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  • Insulin
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Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Pflügers Archiv 400 (1984), S. 413-417 
    ISSN: 1432-2013
    Keywords: Sodium pump ; Na-K ATPase ; Na fluxes ; Vanadate ; Insulin ; Skeletal muscle ; Ouabain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We have measured the effects of concentrations of vanadate ranging between 0.01 and 10 mM on the22Na efflux of frog sartorius muscles. The addition of vanadate had no effects when concentrations lower than 0.5 mM were used; higher concentrations increased Na efflux. The increase was abolished by the addition of ouabain (10−5M). In muscles pretreated with ouabain vanadate did not modify Na efflux. The stimulatory effects of vanadate on Na efflux were also observed in Na-free solutions indicating that the effux of vanadate was not caused mainly either by an increase in the exchange of Na for Na or by an increase in Na entry into the muscle. We also examined the effects of vanadate on muscles immersed in solutions containing 20 mM K+; both vanadate and increased K+ produced stimulations of Na efflux that were additive. Similarly when the effects of vanadate and insulin were measured on the Na efflux of the same muscle, additive effects were found. As the ouabain-sensitive Na efflux in frog muscle is generally agreed to be due to the activity of the Na-K ATPase, our findings suggest that the net effect of vanadate in intact muscle cells is an increase in the activity of the Na pump. Since vanadate affects many enzymes it is quite possible that the stimulatory action is not due to a direct effect on the Na-K ATPase but may be mediated through an intermediary step. Regardless of the specific mechanism, it is evident that, our results as well as other findings in the literature, strongly indicate that Na pumping by intact cells can be increased by vanadate administration. Hence it is not justified to attribute the physiological modifications caused by vanadate administration to blockade of the Na-K ATPase unless the attribution is justified by specific experimental evidence.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1432-0428
    Keywords: Insulin ; insulin antibody ; immunogenicity ; immune response genes ; haemocyanin ; HLA ; DR7 ; C2 ; C4 ; factor B ; Gm ; C-peptide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Seventy-nine patients were observed prospectively during their initial period of treatment with conventional bovine insulins. Insulin antibody levels 6 months after starting insulin therapy did not correlate with age, gender or β cell function at onset of treatment. Patients who required soluble insulin in addition to isophane insulin developed higher levels of insulin antibody. Patients bearing the HLA-B8, DR3 and C4AQO alleles had lower levels of insulin antibody, whereas those bearing DR7 produced significantly higher levels. Other alleles at the C4A, C4B, C2, factor B or Gm loci did not appear to have a significant effect on insulin antibody production. The hyporesponsiveness of B8/DR3/C4AQO-positive individuals probably reflects a non-specific abnormality of immunity whereas the enhanced responsiveness of those positive for DR7 suggests the presence of a specific immune response gene for insulin
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-0428
    Keywords: Insulin ; 3-hydroxy-3-methylglutaryl coenzyme A ; sterol synthesis ; human mononuclear leucocytes ; post-transcriptional regulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Incubation of freshly isolated human mononuclear leucocytes in lipid-depleted serum for 4 h resulted in a two-fold increase in 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) reductase activity. Insulin, when added to the incubation medium at concentrations of 10 and 100 nmol/l at zero time, caused additional increases in the enzyme activity of 30% and 37%, respectively. The hormone action was not immediate because no effect was observed when insulin was added at 4 h and activity examined thereafter. Under these conditions sterol synthesis from 14C-acetate and tritiated water was strictly proportional to the activity of HMG-CoA reductase. Cycloheximide (20 μg/ml), a translational inhibitor of protein synthesis, prevented the insulin-mediated increase in the enzyme activity and the incorporation of 14C-acetate into sterols. Cordycepin (50 μg/ml) inhibited messenger RNA synthesis by 〉 50%, but had no inhibitory effect on the induction of HMG-CoA reductase and sterol synthesis. Low density lipoprotein (80 μg protein/ml) and complete serum blocked the induction of the enzyme and sterol synthesis from 14C-acetate caused by lipid-depleted serum. The insulin-effect, however, remained unchanged. The results suggest that insulin may regulate the de novo synthesis of HMG-CoA reductase and accordingly sterol synthesis at a post-transcriptional level.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 27 (1984), S. 373-378 
    ISSN: 1432-0428
    Keywords: Insulin ; administration and dosage ; therapeutic use ; insulin infusion devices
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The tendency of insulin to form insoluble aggregates is a major obstacle to the development of implantable insulin infusion systems for treatment of insulin-deficient diabetic patients. A test system was developed to examine the kinetics of insulin aggregation under controlled conditions of temperature, vibration and contact material in an effort to provide design criteria for minimising aggregation. The contact materials tested were all potentially suitable for pump reservoirs on engineering criteria and included metals (stainless steel, titanium and a titanium alloy) and various plastics (polypropylene, polytetrafluoroethylene, Polyvinylchloride, polyamide, cellulose butyrate and silicone elastomer). The rate of insulin aggregation was markedly affected by the nature of the contact material. Hydrophilic materials, particularly polyamide and cellulose butyrate (2% of total insulin aggregated after 96 h vibration), appeared more compatible with insulin stability than did hydrophobic ones, such as polypropylene (16% aggregation) and Polyvinylchloride (37% aggregation). A specially formulated ‘pump’ insulin preparation, stabilised by addition of polyethylenepolypropyleneglycol, was significantly superior (three to five times more stable) to a regular neutral insulin formulation under most, but not all, conditions. Standard clinical syringes (polypropylene) performed poorly with both insulin formulations but especially with the neutral regular insulin (100% aggregation after 96 h vibration). In addition to physical aggregates, significant amounts (5%–30%) of the insulin remaining in solution were no longer detectable by immuno- or receptorassay in all materials tested. Appropriate combinations of insulin formulations and materials can minimise insulin aggregation and denaturation, but since the mechanisms involved are as yet poorly understood, realistic testing of proposed reservoir components and insulin formulations must be a prerequisite in insulin infusion pump planning and design. These testing procedures should be designed to test for denaturation in solution as well as for precipitation of insulin.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1432-0428
    Keywords: Insulin ; gastric inhibitory polypeptide ; insulin sensitivity ; glucose tolerance ; diabetes ; diet ; fat ; rate of carbohydrate digestion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The present study examined the acute effects of coingestion of fat (37.5 g) on the post-prandial metabolic responses to 75 g of carbohydrate which was either slowly absorbed (lentils) or rapidly absorbed (potatoes). Co-ingestion of fat resulted in a significant flattening of the post-prandial glucose curves, the effect being more pronounced for the rapidly absorbed potatoes. This was probably due to delayed gastric emptying. However, the post-prandial insulin responses to either carbohydrate were not significantly reduced by fat, suggesting that the insulin response to a given glucose concentration was potentiated in the presence of fat. The gastric inhibitory polypeptide (GIP) responses to both carbohydrates were greatly increased in the presence of fat. To investigate further the possible roles of GIP in the entero-insular axis, a 5-g bolus of glucose was injected intravenously 1 h after lentils ± fat. This was sufficient to raise the glucose levels above the threshold reported for GIP to potentiate insulin secretion. However, despite the large differences in circulating GIP levels, the insulin response to glucose was not affected by the presence of fat. These results suggest that (1) the rate of absorption of carbohydrate is a major determinant of post-prandial metabolic responses even in the presence of fat, (2) fat-stimulated GIP secretion does not potentiate glucose-induced insulin secretion, and (3) the potentiation of the insulin response to glucose when carbohydrate is co-ingested with fat is consistent with the well-documented insulin resistance associated with high fat diets.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    European journal of pediatrics 142 (1984), S. 179-185 
    ISSN: 1432-1076
    Keywords: Craniopharyngioma ; Growth ; Insulin ; Neurosurgery ; Radiotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Management of craniopharyngiomas is still controversial. 28 children with this tumor were studied. GH deficiency was present in 22 patients following surgery, 10 of these GH-lacking patients had normal or accelerated growth (usually associated with rapid weight gain) postoperatively. Somatomedin levels were normal in three of six normally growing patients. After craniotomy their basal and TRH-stimulated prolactin levels were in the normal range, but their insulin secretion was markedly increased. Postoperatively there was a significant correlation between peak insulin levels following arginine infusion and growth velocity in all patients. Complete tumor removal could be performed in 28% of our patients. Altogether 36% of all patients had at least one tumor recurrence. Recent literature with the addition of our series showed tumor recurrence in 22% of patients with “total” tumor excision and in 72% of patients with partial tumor removal. Radiotherapy seems to be capable of destroying craniopharyngioma tissue. The recurrence rate was only 26% in patients with subtotal excision plus radiotherapy. Unless radical tumor removal can be attempted with safety, subtotal tumor removal plus radiotherapy appears to be the treatment of choice for craniopharyngioma.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Intensive care medicine 10 (1984), S. 209-211 
    ISSN: 1432-1238
    Keywords: Amitriptyline ; Hydrocortisone ; Insulin ; Prenalterol ; Cardiac failure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A case of severe amitriptyline poisoning with grade IV coma, seizures, bradycardia and hypotension who did not respond to dopamine was successfully treated with prenalterol, a new cardioselective β-agonist. The case is discussed with respect to plasma concentrations of dopamine, prenalterol and amitriptyline. Prenalterol, hydrocortisone and insulin may be useful as inotropic agents in tricyclic poisoning where dopamine fails to provide an adequate response.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1432-2013
    Keywords: Biological transport ; Insulin ; Energy metabolism ; Epinephrine ; Endocrinology ; Albuterol (salbutamol) ; Active sodium-potassium transport ; Muscle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The total metabolic energy expenditure associated with active Na−K-transport over the first 20 min of stimulation with insulin, adrenaline or salbutamol (ΔHmNa−K) was determined from direct calorimetric and tracer ion flux measurements in isolated muscles at rest. The reversible work performed by the Na−K-pump during the same interval of time (WrevNa−K) was calculated as the product of the ouabain-suppressible Na−K transfers and the mean free energy increase imparted to the two ions as they are transported against their electrochemical gradients across the plasma membrane. Comparison of membrane potential and intracellular Na and K concentrations before and after the stimulations indicated that part of WrevNa−K had contributed to increase the ion electrochemical gradients in the preparation (i.e. had not been lost as heat) during the 20 min period. Accordingly, the maximum value of ΔHmNa−K was taken as the sum of the ouabain-suppressible heat production and WrevNa−K. Following stimulation with insulin, adrenaline or salbutamol this maximum corresponded to 10, 10 and 12% respectively, of basal metabolism. Under the same three conditions, the minimum “energetic efficiency” of the active Na−K-transport process, defined as the ratio between WrevNa−K and maximum ΔHmNa−K, was 35, 41 and 38%, respectively.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular medicine 62 (1984), S. 523-530 
    ISSN: 1432-1440
    Keywords: Neurotensin ; Gastrointestinal hormones ; Gastric secretion ; Pancreatic secretion ; Motility ; Insulin ; Glucagon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neurotensin is a tridecapeptide originally isolated and characterized from bovine hypothalamus and later, in identical form, from bovine and human intestine. In the rat about 85% of immunoreactive neurotensin is found in the gut and about 10% in the brain. When an antibody specific for the amino terminal region of neurotensin was used the highest concentrations were found in the mucosa of the ileum, while an antibody specific for the biologically active region, the carboxyl terminus, also detected large amounts in the mucosa of the upper gastrointestinal tract. After a meal neurotensin — as measured by carboxyl terminal antibodies — rises after 5 min, a time in which the chymus has not yet reached the ileum, the main source of whole neurotensin. It is therefore possible that the carboxyl terminal molecules of neurotensin, found in the upper gastrointestinal tract, play an important physiological role. In plasma, neurotensin is rapidly degraded into smaller amino terminal and therefore biologically inactive molecules. Increases of carboxyl terminal neurotensin have been found in plasma in only a very few studies. The nature of this immunoreactive material has not yet been established. Therefore, the physiological role of neurotensin as a circulating hormone is unknown. Potential actions of neurotensin include thermoregulation, regulation of hormone release from brain (pituitary hormones) and gut (glucagon, insulin, somatostatin, pancreatic polypeptide), increase of vascular permeability, vasodilatation, inhibition of gastric acid secretion, stimulation of pancreatic secretion and changes of gut motility from the fasting to the fed type.
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  • 10
    ISSN: 1432-1440
    Keywords: Aldosterone ; Glucose ; Insulin ; Potassium ; Renin-angiotensin system ; Cortisol ; Captopril
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Glucose loading is known to cause acute suppression of plasma aldosterone and stimulation of plasma renin activity. The relative contribution of variations in circulating angiotensin II to the regulation of aldosterone secretion following glucose loading was assessed in ten normal subjects. The effects of a standard oral glucose loading test (100 g) on plasma concentrations of glucose, insulin, potassium, aldosterone, renin activity and cortisol were studied (a) under basal conditions, and (b) after inhibition of angiotensin II with the converting enzyme inhibitor captopril (50 mg t.i.d. during 3 days). Under basal conditions the acute increase in plasma glucose and insulin after glucose loading was accompanied by a significant decrease (P〈0.01) in plasma cortisol and aldosterone and by a significant increase in plasma renin activity (P〈0.01); plasma potassium was decreased slightly but not significantly. Following captopril treatment preloading plasma renin activity was increased significantly, most probably reflecting an effective reduction of angiotensin II. Glucose loading caused a similar suppression of plasma aldosterone, as observed under basal conditions. This observation suggests that renin activation does not substantially contribute to the acute regulation of plasma aldosterone after an oral glucose load.
    Type of Medium: Electronic Resource
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  • 11
    ISSN: 1433-8580
    Keywords: Oscillations ; Insulin ; Glucose
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The present study was designed to determine the effect of low dose continuous and oscillatory intraportal insulin infusions upon subsequent glucose-induced insulin release. In overnight-fasted and anesthetized rats with indwelling catheters in the jugular vein, carotic artery, and mesenteric vein insulin was infused intraportally for 3 h via the mesenteric vein catheter at a continuous rate of 45 µU/kg·min, or the same amount of insulin was administered at alternating high (72 µU/kg·min) and low infusion rates (18 µU/kg·min), respectively, in 2-, 4-, 8-, and 16-min cycles (oscillatory infusions). Another group received a continuous infusion of saline. Glucose (0.4 g/kg) was given i.v. 30 min after the end of the insulin or saline infusion. During the 3-h infusion of insulin or saline the peripheral glucose level remained unchanged in all groups. In response to the i.v. glucose load peripheral arterial plasma insulin levels were significantly elevated after preceding oscillatory infusions compared to the continuous insulin infusion. As compared to the group receiving saline the glucose-induced insulin response after continuous insulin infusion was significantly reduced. The plasma glucose responses were not different except for inexplicably elevated glucose levels in the 4-min cycle group. No difference was observed for plasma glucagon levels in all groups. The present data demonstrate an augmented responsiveness of theβ-cell to glucose after a preceding oscillatory infusion of insulin and an impaired responsiveness to glucose after continuous insulin infusion. This indicates that an oscillatory insulin release might be of importance for an adequate regulation ofβ-cell function.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 53 (1984), S. 267-273 
    ISSN: 1439-6327
    Keywords: Exercise ; Triglycerides ; Free fatty acids ; Glycerol ; Insulin ; Catecholamines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Metabolic and hormonal responses to prolonged treadmill exercise in dogs fed a fat-enriched meal 4 h prior to the exercise were compared to those measured 4 h after a mixed meal or in the postabsorptive state. Ingestion of the fat-enriched meal caused significant elevations in the resting values of plasma triglyceride (TG), free fatty acid (FFA), and glycerol concentrations. A reduction of the plasma TG concentration (from 1.6±0.2 to 1.1±0.10 mmol·l−1,P〈0.005) occurred only in dogs exercising after the fat-enriched meal. No significant changes in this variable were noted in dogs fed a mixed meal, whilst in the postabsorptive state exercise caused an increase in the plasma TG level (from 0.42±0.03 to 0.99±0.11 mmol·l−1,P〈0.01). The exercise-induced elevations in plasma FFA and glycerol concentrations were the highest in the dogs given the fat-enriched meal. Plasma glycerol during exercise correlated with the initial values of circulating TG (r=0.73). The plasma FFA-glycerol ratio, at the end of exercise was lowest in the dogs taking the fat-enriched meal (1.39±0.19), suggesting an increased utilization of FFA in comparison with that in the postabsorptive state (3.27±0.37) or after a mixed meal (2.88±0.55). Basal serum insulin (IRI) concentrations were similarly enhanced in dogs fed fat-enriched and mixed meals, and they were reduced to control values within 60 min of exercise. Plasma adrenaline and noradrenaline concentrations correlated with time of exercise (r=0.84 andr=0.96, respectively) and were unaffected by the nutritional modifications. It is concluded that ingestion of a single fat-enriched meal considerably modifies the exercise-induced changes in lipid metabolism. The pattern of changes in plasma TG, FFA, and glycerol concentrations indicates an enhanced hydrolysis of plasma chylomicron-TG, suggesting that this lipid source may contribute markedly to exercise metabolism.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 52 (1984), S. 426-430 
    ISSN: 1439-6327
    Keywords: Apoproteins ; Lipoproteins ; Insulin ; Blood lactate ; Physical training
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Eight well-trained males were studied before, during and after 6 months of a progressively increased amount of endurance training in order to elucidate the effects on the apoproteins and apo-lipoproteins. Initially high HDL-cholesterol levels were revealed (1.62±0.15 mmol×l−1, mean ± SE.). After a transient but not significant, slight decline at the onset of the increased training program (1.57±0.06 mmol×l−1) HDL-cholesterol increased gradually to the end of the training period (1.92±0.12 mmol×l−1). There was an increased aerobic capacity as judged by maximal oxygen uptake and by lactate concentration during standardized submaximal work. However, at the end of the training period, a levelling off in maximal oxygen uptake was revealed, while HDL-cholesterol was still increasing. The present data demonstrate that HDL can be influenced by training at all levels of aerobic capacity.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 53 (1984), S. 57-62 
    ISSN: 1439-6327
    Keywords: Muscle glycogen ; Time sequence ; Free fatty acids ; Insulin ; Exercise in humans
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary To evaluate the metabolic and hormonal adaptations following a rapid change in muscle glycogen availability, 14 subjects had their muscle glycogen content increased in one leg (IG) and decreased in the other (DG). In group A (n=7), subjects exercised on a bicycle ergometer at 70% maximal oxygen uptake for 20 min using the DG leg. Without resting these same subjects exercised another 20 min using the IG leg. Subjects in group B (n=7) followed the same single-leg exercise protocol but in the reverse order. In order to get some information on the time sequence of these possible adaptations, blood samples were collected at rest and at the beginning and the end of each exercise period (min 5, 20, 25, and 40). Results indicated that 5 min after the switch from the DG leg to the IG leg. transient increases in plasma free fatty acids (1.20 to 1.39 meq·l−1) and serum insulin (10.1 to 12 mU·l−1) concentrations occured. Between minute 25 and 40 of exercise, the DG to IG switch was accompanied by a decrease in free fatty acids and glycerol concentrations as well as an increase in lactate levels. An opposite response was observed in the IG to DG condition during the same time span. Plasma norepinephrine, epinephrine, glucagon, and serum cortisol concentrations were not significantly affected by the leg change. These results suggest a rapid preferential use of muscle glycogen when available and a time lag in the response of the extramuscular substrate mobilization factors.
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  • 15
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 169-174 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Water-ground Phlogopite micas were classified into narrow particle-size distributions containing flakes with well-defined diameters and thicknesses in order to evaluate the influence of particle size and flake aspect ratio on the mechanical properties of mica-filled polypropylenes, For the purposes of comparison, most of the injection-molded specimens contained 40 percent (by weight) mica. As expected, the flexural and tensile modulus values increased in proportion to the aspect ratio over the range from 30 to 60 to a maximum of 8 GPa. The measured tensile strengths of the mica-filled polypropylenes increased substantially as the flake diameter became smaller, but did not correlate with the flake aspect ratio. The attainable properties were frequently dependent upon the method of mixing, and considerable care was necessary to ensure proper dispersion and adequate coupling. Intensive mixing, as in a Gelimat Mixer, may cause in situ delamination and particle-size reduction of the mica filler particles, leading to a marked increase in tensile strength of the resulting composite. The mica-filled compounds could be reprocessed many times without significant loss of properties, particularly compounds having mica particles less than 40 μm in diameter. The fracture energies (notched Izod) and the heat-distortion temperatures were not appreciably influenced by the size or aspect ratios of the mica within this range. Increased fracture toughness could be achieved by reducing the mica concentration or employing a polypropylene copolymer. Guidelines are presented to indicate the preferred characteristics of mica fillers and the influence of mixing conditions on performance.
    Additional Material: 7 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 30-41 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical model has been developed to compute the molecular weight distribution (MWD) in the polyethylene terephthalate (PET) manufacturing process. Unlike the previous efforts, this model takes into account the influence of side reactions and various interchange reactions on MWD. The process of blending of molten polyester chips has also been simulated with a view to calculate the equilibrium MWD as well as the time required to reach the equilibrium MWD. The1 significance of the results has been discussed in terms of industrial operations involving PET polymerization and PET blending.
    Additional Material: 10 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 541-543 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 555-562 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Methods of preparation and of determining miscibility limits for partially miscible binary polymer blends are described. An equation-of-state, theoretical description of this behavior is introduced and the terms describing interactions within the system discussed, Values of these interaction terms are obtained by fitting the models to measured cloud point curves, heats of mixing data, etc. The use of neutron scattering experiments to obtain molecular conformation and interaction parameters is described and a comparison made with values extracted from the thermodynamic measurements.
    Additional Material: 9 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 163-168 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dextran-g-poly(acrylamide-co-sodium acrylates) were prepared by partial hydrolysis of dextran-g-poly(acrylamides) with controlled numbers and lengths of grafted chains. This hydrolysis route proved to be more effective than Ce(IV)-induced cografting of acrylamide and sodium acrylate comonomers onto dextran in producing the desired graft-copolymer structures. The resulting copolymers were characterized and the effects of composition, temperature, ionic strength, and shear rate on dilute solution rheological properties were studied.
    Additional Material: 6 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 194-204 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The formation of polyethylene terephthalate (PET) has been modeled to have reactions with monofunctional compounds, redistribution, and cyclization reactions in addition to the usual polycondensation step. In the final stages, the overall polymerization is mass-transfer controlled and solution of the reactor performance equations have been determined through the orthogonal collocation technique. This technique is found to be considerably more efficient for PET reactors compared to the finite difference method; the use of ten collocation points gives results which are close to the exact solution.
    Additional Material: 11 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 218-225 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This review focuses on a new type of para-catenated aromatic polymer being used in the preparation of high-performance films and fibers of exceptional strength, thermal stability, and environmental resistance, including inertness to essentially all common solvents. Polymers of this type include cis and transpoly(p-phenylene benzobisoxazole) (PBO), and the cis and trans forms of the corresponding poly(p-phenylene benzobis-thiazole)(PBT). The purpose of this paper is to summarize the authors' theoretical work on the structures, conformational energies, intermolecular interactions, and electronic properties of PBO and PBT chains, including the protonated forms known to exist in strong acids. The emphasis is on how such studies provide a molecular understanding of the unusual properties and processing characteristics of this new class of materials.
    Additional Material: 6 Ill.
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  • 22
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(p-phenylene terephthalamide) (PPD-T) films have been prepared by continuous extrusion of liquid crystalline 17 percent PPD-T/sulphuric acid solutions through an annular die followed by coagulation, Films extruded without drawdown exhibit some polymer chain orientation in the machine direction. This is increased by uniaxially drawing down films. Films produced with a lubricated conical mandrel sitting between the die and the coagulation bath exhibit an equal biaxial orientation. The uniaxially oriented films exhibit highly anisotropic mechanical properties, while the mandrel-produced film exhibits balanced properties. Heat treatment at 350°C results in significant enhancement of the tensile strength of the mandrel film. Void structures in the films have been investigated by mass density, scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS). Density measurement indicate a void content decreasing with decreasing film thickness and heat treatment. SEM locates micron-size voids in the thickest films, apparently caused by rapid coagulation. SAXS indicates much smaller void sixes which are roughly prolate ellipsoids (long axis in machine direction) for uniaxial films and oblate ellipsoids (short axis in thickness direction) for the mandrel produced films. Various techniques are used to estimate mean void size.
    Additional Material: 17 Ill.
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  • 23
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 278-286 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(vinyl chloride) (PVC) and its blends with polybutadiene-acrylonitrile (NBR) (containing 21.7 weight-percent acrylonitrile (AN), a heterogeneous two-phase system; and containing 41.6 weight-percent of AN, a homogeneous one-phase system) and with polyethylene-vinyl acetate (EVA) (containing 45 weight-percent of vinyl acetate (VA), a heterogenous two-phase system; and containing 65 weight-percent VA, a homogeneous one-phase system) were UV-irradiated (at 3500 Å UV-light (solar spectrum)). After UV irradiation the kinetics measurements were made of the formation of hydroperoxy (OOH) and carbonyl (CO) groups and the changes of mechanical properties: tensile strength, elongation to break, and impact energy. As a result of the photooxidative degradation of PVC blends, decreases of mechanical properties were observed. The effects are more severe in PVC/NBR blends, which contain unsaturated bonds (polybutadiene segments) than in the case of PVC/EVA. The phase structure plays an evident role on the UV degradation only of PVC/NBR blends. The photostability of PVC blends can be slightly improved by introducing Tinuvin P or Ni-chelates photostabilizers.
    Additional Material: 8 Ill.
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  • 24
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 292-292 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 25
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 319-327 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An investigation was carried out in order to study the effect of prestrain on the subsequent crystallization of a specific copolyester based on lactic and glycolic acid. This polymer, which can be easily quenched into an amorphous glass, has a Tg of 43°C and when in crystalline form has a melting point of 210°C. Using amorphous films, samples were prestrained to various levels at temperatures not far above Tg. In some cases films were immediately quenched at the prestrain level so as to retain the elongation while others were allowed to immediately retract whereby they showed a relatively small degree of permanent Set. Utilizing birefringence, quenched samples whose initial elongation was maintained showed linear behavior with prestrain while those that retracted showed essentially zero birefringence until a prestrain of about 150 percent after which a small degree of positive birefringence resulted. Wide angle x-ray diffraction (WAXS) showed no signs of crystallinity in all cases. These same films were then quickly taken to 150°C and rapidly crystallized. Again, one series of the prestrained samples were in the elongated state during crystallization whereas the second series was unrestrained during crystallization. Using microscopy and small angle light scattering (SALS), the morphological textures of these crystallized films were investigated. In all cases, spherulitic textures were observed of equivalent size up to a value of about 200 percent elongation the spherulite size systematically decreased with the prestrain an increase in clearly showing that prestrain had a pronounced effect upon the nucleation density. Increasing draw rate displayed a similar effect on nucleation density. Since spherulite size was noted to be the same in either series, it indicated that nucleation was induced as a result of the prestrain and remained irrelevant of whether the sample was allowed to relax or not. The morphology above the transitional state was similar to row structure common to polymers crystallized in the oriented state. WAXS and birefringence was applied to the crystallized materials and it was found that up until the transitional zone, no crystal orientation was observed in either series indicating that although nucleation density was strongly affected up until that point, no orientation was retained within the sample upon crystallization. A simplified model is used to explain the observed results.
    Additional Material: 16 Ill.
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  • 26
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 965-973 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method based on network theory is developed for characterizing molecular orientation in amorphous polymers. The proposed procedure gives not only the orientation distribution function for the chain segments in the polymer network (and hence the average orientation) but also a quantitative measure of how this orientation is distributed among the various types of entanglement junctions. The orientation of chain segments can be characterized by two parameters, one which gives the average orientation and another which reflects how much orientation is concentrated in long time entanglement junctions. The new method of characterizing orientation is used to interpret tensile strength data for both brittle and ductile failures.
    Additional Material: 10 Ill.
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  • 27
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 28
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1025-1025 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 29
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1035-1042 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study of the crystalline orientation, light transmission, and surface roughness of polyethylene tubular film prepared in our laboratories is presented. The present studies were primarily carried out on low-density (LDPE) and linear-low-density (LLDPE) polyethylene films. The optical properties of a few films of high-density polyethylene (HDPE) prepared for a previous study of morphology were characterized for comparison to the LDPE and LLDPE films. Wide angle X-ray diffraction and birefringence were used to characterize orientation. Both the LDPE and LLDPE films exhibited crystalline texture in which the b-axes tended to be perpendicular to the film surface and the a-axes had some tendency to align with the machine direction. The c-axes tended to be concentrated in the plane of the film with nearly equal biaxial orientation with respect to the machine and transverse directions. Little variation in the crystalline orientation was found with changes of process conditions in the range studied. Birefringence results indicate that the amorphous regions developed an orientation in which the chains tend to be normal to the film surface. The majority of light scattering from these films and a series of HDPE films was from the surface and not from the film interior. The transmission coefficient for the surface contribution was found to be a monotonic decreasing function of the standard deviation of the surface height obtained from surface profiles measured by profilometer. The surface asperites were largest for the HDPE and smallest for the LDPE samples. The intensity of both the surface and interior contributions to the scattering increased with increasing frostline height, i.e., a slower cooling rate. As draw-down ratio and blow-up ratio increase the scattering contribution from the film interior decreases but the contribution from the surface increases somewhat. These effects are discussed in terms of the changes in crystalline morphology and surface roughness produced by flow defects generated during extrusion.
    Additional Material: 11 Ill.
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  • 30
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1064-1070 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Stress-corrosion data for poly(ethylene terephthalate) reinforced with short glass fibers are provided under various environments and the microscopic observations are compared with the lifetime data. It is concluded that the lifetime behavior coincides with the microstructural features; this aspect is quantified by the statistical analysis.
    Additional Material: 17 Ill.
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  • 31
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 442-454 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The two major problems encountered in industrial liquid-phase addition polymerization are: the heat released by highly exothermic reactions and the great increase in viscosity with conversion. The high rate or heat generation, coupled with the low thermal diffusivity of the reacting system, often lead to thermal runaway. Even with the process kept under marginal control, large temperature variations broaden the product molecular-weight distribution. Temperature control is particularly difficult in the Trommsdorff region, where reaction rate rapidly increases as temperature rises and viscosity builds up. A two-stage process is developed in this work to attack these problems and to achieve continuous operation of poly(methyl methacrylate) bulk polymerization. This process utilizes a continuous stirred-tank reactor (CSTR) as a first-stage prepolymerizer and a spray tower as the second-stage finishing reactor. Use of a CSTR offers good temperature control and product uniformity during the early stages of reaction and eases delivery of the reacting system to the second stage at the desired conversion and molecular-weight level. Spraying the partially polymerized mixture into the tower as fine droplets prior to the onset of gel effect eliminates the problems of transporting, agitating, and mixing a reacting system with a rapidly increasing viscosity. Heat of reaction is efficiently removed by a countercurrent stream of nitrogen in the tower, in direct contact with the falling droplets. The high surface-to-volume ratio of these small droplets facilitates heat transfer, and the problem of heat buildup can be efficiently controlled. Products from the bottom of the tower can then be melt-processed by conventional methods, such as extrusion. Experiments performed in the laboratory have demonstrated the feasibility of this proposed concept. Process optimization was in no way achieved due to serious space and equipment limitations. The process was thus further examined by computer simulation and model parameter sensitivity study. A practical design was recommended based on the model predictions.
    Additional Material: 21 Ill.
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  • 32
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 473-481 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An experimental study was conducted on the injection molding of a thermosetting polyester resin. For the study, a general-purpose unsaturated polyester resin was used, with benzoyl peroxide as initiator. A differential scanning calorimeter (DSC) was used for studying the curing kinetics, under isothermal curing conditions. A plunger-type injection-molding apparatus was constructed, and a rectangular mold cavity with glass windows on both sides was constructed, which permitted us to record on a film the changes in stress birefringence patterns in the mold cavity during the molding operation (i.e., during the isothermal cure, post cure, and subsequent cooling), using a crossed circular polariscope. The injection-molded specimens were used to determine the distribution of the degree of cure at various positions in the flow direction, and to relate the degree of cure to the dynamic mechanical properties.
    Additional Material: 16 Ill.
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  • 33
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1240-1244 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Standard test specimens of mortar were cured under water for 15 days to achieve satisfactory strength. They were dried without allowing dehydration reactions to occur, evacuated to 40 millimeters (mm) Hg, and impregnated with a styreneacrylonitrile comonomer, which gives the highest strength after polymerization. Positive pressure of 0.6 N/mm2 was applied and thermal catalytic polymerization was carried out. Optimum initiator concentration was found to be 2 percent. Strength (compressive and tensile) increases with polymerization temperature up to 120°C, above which rapid deterioration occurs due to monomer loss, production of short chains with high polymerization rates, and the possibility of polymer degradation at high temperature. Optimum polymerization period of' 10 hours was selected. Inexpensive methods for field polymerization were tried at 95°C. Hot water yields a strength more than double that obtained with a, flow of hot air and about 80 percent of that obtained radiolytically. While hot air accelerates evaporation, hot water forms a hydraulic head above the capillaries and decreases the monomer losses tremendously.
    Additional Material: 8 Ill.
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  • 34
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The absorption of water vapor by propellants based on hydroxy-terminated polybutadiene and an isocyanate from atmospheres of increasing relative humidities, and the swelling index of the propellant which had absorbed various proportions of water, were measured in an attempt to establish the extent of hydrolytic damage. The method was found incapable of assessing such damage, but it was shown that there was no measurable absorption of vapor below 92 percent relative humidity (RH). The MEK/polymer and toluene/polymer interaction parameters were determined.
    Additional Material: 3 Ill.
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  • 35
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 673-685 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The hierarchy of mathematical models of injection molding is reviewed. Compatibility of the models of the hierarchy, usefulness of simultaneous applications of models formulated on several different levels of the hierarchy and compatability between physical approximations leading to the formulation of a model, and mathematical approximations used to solve numerically the governing equations of the model are discussed. This review is intended to facilitate the search for a model that is best suited to a given need and to indicate future research.
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  • 36
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 716-721 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 37
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 737-749 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper discusses some new mechanical and small angle neutron scattering (SANS) data on glassy polymers, both thermoplastics and thermoset resins, from the point of view of dislocation-like defects introduced in the molecular chain arrangement by deformation. In the pre-yield stage, a new parameter, the work-hardening rate K is introduced and its measurement is defined. Experiments are reported which show that K can be used as a very sensitive probe for microstructural changes during physical aging or curing. In one hand, the theory of yielding is revisited to make clear how dislocations and their propagation in polymers depend on specific features like entanglements and chain stiffness. On this basis, experimental internal stresses and activation volumes at yield (i.e., the temperature slope of yield stress) are accounted for. On the other hand, SANS data provide us with experimental evidence at the scale of 10 to 20 Å of the dislocation nature of the molecular “shear defects” introduced in the polymer by deformation. Finally, temperature is known to have a pronounced influence on yield processes. It is shown that two distinct deformation modes exist below and above a critical temperature Tc. Above Tc, a dislocation climb, which probably involves β-processes, gives rise to a “diffusional” deformation mode where chains within a (diffuse) shear band are no longer oriented. A tentative formalization of this behavior, and its relation to the small strain creep of polymers, are then presented.
    Additional Material: 9 Ill.
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  • 38
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 724-736 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The deformation behavior of three polymers, polyethylene terephthalate (PET), polymethylmethacrylate (PMMA), and linear polyethylene (LPE) is considered in terms of two key factors, the stretching of a molecular network and the influence of thermally activated processes. In PET the observation of a natural draw ratio leads to studies of shrinkage, shrinkage force, and optical birefringence to define the nature of the network. The network is further exemplified by measurements of the molecular reorientation in deformation bands, spectroscopic studies of molecular orientation in drawing, and the concept of a true stress-strain curve. Yield and plastic deformation are also to be considered as thermally activated processes, but it appears that a major part of the flow stress is associated with the stretching of the molecular network. In PMMA the concept of a true stress strain curve also appears to be valuable, but the possibility of network breakdown during deformation has to be admitted as an extra complexity. In LPE the concept of a molecular network embracing both crystalline and non-crystalline material is helpful in understanding the drawing behavior. There is also direct evidence for the existence of a network from measurements of shrinkage and shrinkage force, and the existence of a true-stress strain curve. However, the dominant contribution to the flow stress now appears to come from thermally activated processes, with a key contribution from a small activation volume process which is tentatively associated with slip in the crystalline regions.
    Additional Material: 23 Ill.
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  • 39
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 886-894 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Internal friction has been measured by torsion at 1 Hz during tensile tests performed on glassy polycarbonate at room-temperature. Steady-state flow and transient effects have been studied during continuous tensile tests and strain-rate changes. During steady-state, internal friction and flow-stress vary in a similar way with strain-rate. But during transients, internal friction varies continuously while flow-stress passes through a maximum (or a minimum). These results are interpreted assuming that non-elastic deformation of glassy polymers requires some microscopic discontinuous processes such as motion of defects. Two parameters are considered: the velocity v and the density ρ of mobile defects. Assuming that the former is directly related to the flow stress, it has been shown that internal friction is related to the density of mobile defects ρ. This feature is used to interpret the different stages of a tensile test curve. Activation volumes for both velocity and density of mobile defects are calculated from experimental data.
    Additional Material: 13 Ill.
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  • 40
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 915-920 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The molecular kinetic theory near the glass transition, bused on the existence of free volume distribution, is extended to incorporate the effects of stress and stress rate. The fundamental equations for the volume relaxation and recovery in stressed amorphous polymers are derived in accordance with the balance of nonequilibrium statistical entropy. Using these kinetic equations, an earlier nonequilibrium criterion for the glass transition temperature, Tg, is generalized to include the effects of stress and stress rate. In contrast to the prevalent thinking toward free volume theories, an explicit expression between Tg and stress is developed and reveals that Tg does not continue to increase at all pressures but levels off to a “universal” asymptote at very high pressure (〉10 K bars). The expression is applicable to any tension and compression stress conditions. A comparison between theory and experiment under constant stresses determines the activation volume tensor which reveals the molecular mechanism relating Tg and the plastic yield of glassy polymers.
    Additional Material: 3 Ill.
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  • 41
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Paper properties of the thermochemical pulp modified by ozonation and grafting with styrene, acrylamide or their mixtures have been studied. Paper sheets, prepared by hot pressing from ozonated and grafted pulps showed improvement in: wet breaking length; dry breaking length; burst and dimensional stability.
    Additional Material: 5 Ill.
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  • 42
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 608-611 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A commercial polyarylate (PAr), a copolyester of Bisphenol-A with 50 percent terephthalate-50 percent isophthalate, has been characterized by means of a combination of gel permeation chromatography and viscometry. It has been studied as first component of a series of polymer blends. The presence of either one glass transition temperature (Tg) or two has been used as a criterion to determine the miscibility of each blend. In some cases, the possible incidence of transesterification reactions has been considered.
    Additional Material: 3 Ill.
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  • 43
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 624-625 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 3 Ill.
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  • 44
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 645-651 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The residence time distribution (RTD) in a fully intermeshing, corotating twin screw extruder was determined with a stimulus-response technique. In addition to varying three process parameters (i.e. throughput, screw rotational speed, and barrel temperature), two screw configurations were also studied: one containing four kneading block mixing sections, and the other consisting only of regular screw bushings. Although screw configuration was an important variable, it was found that for both configurations the throughput had the largest effect on RTD. The screw rotational speed was second in importance, and the barrel temperature change produced no effect.A fluid mechanical model based on the fluid flow in a partially-filled rectangular channel was used to explain the experimentally observed dependence of RTD on the process parameters. Reaction engineering approaches were adopted to compare the RTD results of two screw configurations with two idealized flows.
    Additional Material: 9 Ill.
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  • 45
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 686-691 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Some aspects of injection-molding dynamics were studied using a laboratory injection-molding machine operated under the control of a microprocessor-based servocontrol system. Two types of experiments were performed: deterministic tests which introduced step changes in the servovalve opening and stochastic tests using pseudo-random binary sequence (PRBS) perturbations of the servovalve. Deterministic models were written for the hydraulic and nozzle pressures which were in good agreement with the experimental data. A stochastic transfer function-noise model was obtained for the nozzle pressure, but an adequate model was not found for the hydraulic pressure. The agreement between the nozzle pressure stochastic model and the corresponding step test model was satisfactory.
    Additional Material: 9 Ill.
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  • 46
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 707-715 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A general-purpose finite element program has been used to simulate the flow of Newtonian, power-law, and viscoelastic fluids in the entry and exit regions of a slit die. It was found that shear-thinning increases the entrance correction while it decreases the exit correction. Shear-thinning reduces the size of the small corner vortex that forms in the entry flow of a Newtonian fluid. The swelling ratio had a value of 1.196 for Newtonian fluids and decreased as the value of the power-law index decreased. Viscoelastic calculations were performed using the Criminale-Ericksen-Filbey (CEF) constitutive equation. Convergence of the iterative scheme was unattainable for Deborah numbers above 1.0. The results showed a decrease of the entrance correction and an increase of the exit correction with elasticity. Extrudate swell first decreased slightly and further increased with the Deborah number.
    Additional Material: 8 Ill.
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  • 47
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 761-769 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: As crazes grow in areal extent they also increase in width. The areal growth involves craze tip advance which has been shown to occur by the Taylor meniscus instability. Craze widening, at least for air crazes, occurs by drawing more fibrillar material from the craze-bulk polymer interfaces at essentially constant extension ratio. Simple arguments will be given to predict the scale of the fibrillation in terms of the stress S at the craze tip and interfaces and an effective polymer surface energy (Γ) where:\documentclass{article}\pagestyle{empty}\begin{document}$$ {\Gamma = \gamma + {\raise0.5ex\hbox{$\scriptstyle 1$}\kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle 4$}}d \cdot v_E U_b} $$\end{document} which assumes that all entangled chain crossing the surface are broken [γ represents the van-der-Waals (intermolecular) surface energy, d is the entanglement mesh size, vE is the entanglement density, and Ub is the energy required to break a single backbone bond]. These arguments also give the rate of fibrillation as a function of S, a nominal plastic resistance σy and Γ and can explain the fact that the stress for crazing increases relative to that for shear deformation as the entanglement density of the polymer is increased. The geometrically necessary entanglement loss (either by scission as assumed above or by disentanglement- at temperatures just below Tg) that accompanies fibril formation has important consequences for fibril stability. The probability p that a given entangled chain is lost can be computed from simple geometrical considerations knowing the fibril diameter D, its extension ratio λ and the mesh size d; p increases rapidly as Dλ½ becomes comparable to or less than d. These concepts can be tested in blends of high molecular weight polymer with chains of the same polymer that are too short to entangle.
    Additional Material: 6 Ill.
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  • 48
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1174-1179 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Critical strains causing environmental stress cracking of injection-molded poly(acrylonitrile-butadiene-styrene) (ABS) and poly(styrene-acrylonitrile) (SAN) plaques were determined upon exposure to methanol. Measurements were obtained for samples strained either parallel or perpendicular to the melt flow direction and for samples located at various distances from the mold gate. Critical strains were significantly higher in the direction parallel to the melt flow compared to the transverse direction. The degree of anisotropy increased with increasing rubber content. For ABS containing 46 percent rubber, the critical strain at one point was determined to be 2.99 percent in the direction of melt flow, but only 0.47 percent in the orthogonal direction. For this material, critical strains determined parallel to the melt flow decreased with distance from the gate; whereas, critical strains for SAN and ABS containing 30 percent rubber remained essentially constant. Orientation of the plaques was assessed using shrinkage determinations and a thermal conductivity technique. Though a straightforward correlation of orientation with critical strain is observed for ABS, a similar relationship is not observed for SAN. These results suggest that although stress cracking occurs in the glassy matrix of ABS, it is the dispersed rubbery phase which controls the magnitude of strain required to initiate cracking.
    Additional Material: 11 Ill.
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  • 49
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1185-1201 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A basic study of the kinematics, dynamics, and heat transfer occuring during tubular film extrusion of polyethylene is outlined. Three rheologically characterized polyethylenes, a low-density polyethylene (LDPE), a linear-low-density polyethylene (L-LDPE), and a high-density polyethylene (HDPE) were used in this study. The kinematics and stability of the tubular film process were investigated over a wide range of blow-up ratios, drawdown ratios, and frost-line heights. Local deformation rates along the bubble have been determined. Regions of stability and instability are described. Tensions and inflation pressures have been measured and expressed in terms of locol elongational viscosities. Temperature profiles along the bubble were determined and interpreted in terms of local heat transfer coefficients. Positions of crystallization and temperature profiles have been noted and used to estimate rates of crystallization. The characteristics of the LDPE, LLDPE, and HDPE are contrasted.
    Additional Material: 47 Ill.
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  • 50
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 51
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1020-1020 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 52
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1026-1034 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical analysis of bubble growth in an expanding foam is presented. The analysis is based on a cell model whereby the foam is divided into spherical microscopic unit cells of equal and constant mass, each consisting of a liquid envelope (or shell) and a concentric spherical gas bubble. Expansion occurs by diffusion of a dissolved gas from the supersaturated envelope into the bubble. This cell model is capable of describing important qualitative features of a real system of numerous bubbles growing in close proximity to one another, and is intended as the building block of a global analysis of macroscopic foam expansion. The coupled algebraic and differential equations governing the growth of a cell are derived and solved numerically. Five dimensionless parameters are identified for the case of constant temperature and pressure outside the cell, and their effects are demonstrated through computer simulations of the system. Of these parameters, surface tension and initial radius prove to be of relatively little importance in the practical cases considered. The other parameters are the thermodynamic driving force, the cell mass (inversely proportional to the number density of bubbles), and the ratio of characteristic times for mass and momentum transport.
    Additional Material: 7 Ill.
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  • 53
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1277-1282 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper outlines the development of an acoustical technique for measuring the dispersion of an additive in a polymer melt. It included a justification of the use of sound over other interrogating methods and an analysis of the acoustical system's operation. Results for dispersions of liquid or solid additives were shown. It was demonstrated that this system could detect the presence or absence of large particles in melts filled with small particles.
    Additional Material: 15 Ill.
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  • 54
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 55
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    Polymer Engineering and Science 24 (1984), S. 1284-1290 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We discuss the free-energy expressions for homogeneous melts and their blends, based on our hole theory. Equation of state (PVT) and free energy of mixing (ΔGm) are considered from a common point of view without the introduction of additional parameters to pass from the first to the second set of properties. Practical problems arise from the fact that ΔGm represents a difference between large quantities. As illustrations we analyze two typical systems. One is the n - C6 + n - C16 pair where PVT and ΔGm, the latter at atmospheric pressure only, have been studied experimentally. The other is n - C6 with a low and high molecular weight respectively of polyethylene as solute. Here the PVT relations of the components only are known. The effects of intercomponent attractions, temperature, pressure, and molecular weight on phase behavior are investigated. Critical coordinates, lower critical-solution temperatures (LCST) and their pressure dependence are computed. An iso-free volume condition obtains for this dependence where free volume is defined by the hole fraction inherent in the theory. Comparisons with experimental observations and other theoretical computations for different molecular weights are limited by the effect of polydispersity. Moreover, cloud point curves are shown. We finally compute the composition and pressure dependence of the χ-parameter which is implicit in the theory. We conclude with some comments regarding polymer blends.
    Additional Material: 6 Ill.
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  • 56
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    Polymer Engineering and Science 24 (1984), S. 1312-1318 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Blends of polycarbonate/polystyrene (PC/PS), polycarbonate/polypropylene (PC/PP) and ternary blends of the three components (PC/PS/PP) were studied. Extrudate swell of the molten blends increased with increasing concentrations of the minor components and leveled off at characteristic blend compositions. These compositions corresponded to the limits of compatibility as judged by the onset of brittleness in tensile tests. Both PS and PP appear to have some limited practical compatibility with PC. The change in extrudate swell behavior with concentration may be a rapid and convenient test for the effective concentration limits of partially miscible polymers.
    Additional Material: 17 Ill.
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  • 57
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An experimental study of the development of phase morphology in incompatible polymer melt blends of polyethylene/polystyrene (PE/PS), polyethylene/polycarbonate (PE/PC), and polyethylene/nylon-6 (PE/N6) is presented. Different temperatures (180°C, 240°C) of mixing and polyethylene molecular- weight levels were used in the PE/PS studies. Little variation in the cross-sectional phase morphology of the PE/PS extrudates was observed with these variables, though the morphology became finer with increased shear rate/stress in capillary die flow. Variations in the longitudinal morphology are observed with continuous filaments of dispersed phase only arising when the dispersed phase has an equal or lower viscosity than the continuous phase. The PE/N6 and PE/PC, especially the former, give coarser morphologies when the N6 and PC are the continuous phases. This was attributed to larger inter-facial tensions. The effect of viscoelasticity was also discussed.
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  • 58
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 59
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 42-47 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Kevlar 29 fiber has been widely considered for the manufacture of very-long high-performance cables. Due to low transverse strength fiber-on-fiber rubbing leads to rapid deterioration. The usefulness of impregnating Kevlar 29 braids with resin to overcome this drawback has been evaluated by performing reverse bending fatigue tests. Braids of identical construction, one of them being impregnated with a polyurethane resin by a patented process, were fatigued to failure on a purpose-built rig under varying applied loads. Fatigue tests were also carried out to 30 percent and 50 percent of total braid life and residual strength values measured. It was found that high applied loads (∼50 percent of ultimate) lead to premature braid failure dominated by a creep mechanism. Both braids showed similar behavior, although the impregnated braid was superior. At low applied loads, however, where the failure mechanisms was dominated by wear or internal abrasion, it was seen that resin impregnation could increase braid life by a factor of four. Resin impregnation coupled with bending fatigue significantly stiffens braids, as was demonstrated by tensile testing up to braid failure.
    Additional Material: 8 Ill.
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  • 60
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 22-29 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In this article the kinetics of chemical-controlled radical-chain copolymerization have been reduced to pseudohomopolymerization kinetics by introducing the apparent rate constants, The methods for the determinations of the values of the apparent rate constants, mode of termination, and the methods for the calculation of molecular weights and distributions are proposed. The data required for these determinations and calculations are simply obtained by the usual steady-state method. According to the traditional kinetics along with the definitions of the apparent rate constants, these apparent rate constants as functions of traditional rate constants, monomer compositions, and copolymer compositions are derived. Further utilizing the theoretical expressions obtained, we show that the apparent rate constants are the general rate constants for both radical chain homo- and copolymerizations. The bulk radical copolymerizations of methyl methacrylate and styrene at various monomer feed compositions at 60°C are used to test the proposed model. The empirical apparent rate constants obtained are described well, by the following expressions, \documentclass{article}\pagestyle{empty}\begin{document}$$ \beta = 0.997{\rm }F_1 + 0.398{\rm }F_2 + 0.039\left({F_1 F_2 } \right)^{\frac{1}{2}} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ {{k_t^a } \mathord{\left/ {\vphantom {{k_t^a} {\left({k_p^a} \right)}}} \right. \kern-\nulldelimiterspace} {\left({k_p^a } \right)}}^2 = - 0.138 \times 10^4 \left({{{F_1 } \mathord{\left/ {\vphantom {{F_1 } {f_1 }}} \right. \kern-\nulldelimiterspace} {f_1 }}} \right)^2 + 0.354 \times 10^4 \left({{{F_1 F_2 } \mathord{\left/ {\vphantom {{F_1 F_2 } {f_1 f_2 }}} \right. \kern-\nulldelimiterspace} {f_1 f_2 }}} \right) - 0.114 \times 10^4 \left({{{F_2 } \mathord{\left/ {\vphantom {{F_2 } {f_2 }}} \right. \kern-\nulldelimiterspace} {f_2 }}} \right)^2 $$\end{document} and the mode of termination on the combination termination is \documentclass{article}\pagestyle{empty}\begin{document}$$ {1 \mathord{\left/ {\vphantom {1 {{\rm k}_p^a = - 0.132}}} \right. \kern-\nulldelimiterspace} {{\rm k}_p^a = - 0.132}} \times 10^{ - 2} \left({{{F_1 } \mathord{\left/ {\vphantom {{F_1 } {f_1 }}} \right. \kern-\nulldelimiterspace} {f_1 }}} \right) + 0.428 \times 10^{ - 2} \left({{{F_2 } \mathord{\left/ {\vphantom {{F_2 } {f_2 }}} \right. \kern-\nulldelimiterspace} {f_2 }}} \right) $$\end{document} where Kaa and Kta denote the apparent rate constants of propagation and termination, respectively. The term f1(= 1 - f2) stands for the mole fraction of styrene in the monomer solution fed. F1 is the copolymer composition produced at f1. β is the mode of termination.
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  • 61
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The modification of an amorphous random ethylene-propylene rubbery copolymer (EPM) has been accomplished by solution grafting of maleic anhydride molecules promoted by radical initiators, The resulting EPM-g-succinic anhydride (EPM-g-SA) and EPM have been used to obtain binary polyamide 6/EPM or polyamide 6/EPM-g-SA and ternary polyamide 6/EPM/EPM-g-SA blends by melt mixing. The formation of an EPM-g-PA6 graft copolymer during the blend preparation has been assumed. Different blend morphologies were observed by scanning electron microscopy (SEM) according to the nature and content of the rubber used. The tensile mechanical properties and the impact behavior of the prepared blends were investigated and correlated with the SEM analysis of the fracture surfaces. Binary and ternary blends containing 20 percent by weight of total rubber show a significant improvement of the impact properties at low temperature (-20°C) when the rubber is partly or entirely EPM-g-SA. In the case of PA6/EPM-g-SA (80/20) blend these results are related to the presence of rubbery domains of very small size strongly adherent to the PA6 matrix. In the case of 80/10/10 ternary blends, a much more complicated overall morphology is observed. Such morphology is characterized by the presence of large EPM domains, likely containing some EPM-g-PA6 graft molecules acting as an interfacial agent, and domains of EPM-g-PA6 of smaller size strongly adherent to the matrix as in the previous case.
    Additional Material: 11 Ill.
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  • 62
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The Lower Critical Solution Temperature (LCST) of polyethylene (PE), polypropylene (PP), and ethylene-propylene block and random copolymers have been measured in heptanes. A thermogram related to the variation of the turbidity of the solution is obtained between 100 and 210°C. The temperature of the onset of the turbidity peak is defined as the LCST of the system. The width and the area of the turbidity peaks are tentatively associated with the polymer polydispersity and the amount of polymer involved in the phase separation. The thermograms of solutions containing both homopolymers show two distinct turbidity peaks situated at a 70°C interval. Correlations of molecular orientations in the concentrated phase, possible in PE systems but not in PP solutions, are at the origin of the lower LCST values for PE solutions. The LCST of copolymers are situated between those of the homopolymers but the dependence of the LCST on the copolymer ethylene content is different for block and random copolymers. Examples of thermograms are also given for mixtures of copolymers with PE and PP. By analysis of their thermograms, some commercial block EP copolymers were also found to contain PK and PP. This method seems well suited for characterizing polymer mixtures.
    Additional Material: 10 Ill.
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  • 63
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    Polymer Engineering and Science 24 (1984), S. 144-152 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dielectric properties of miscible blends of poly(vinyl chloride) (PVC) and poly(α-methyl-α-n-propy-β-propiolae-tone) (PMPPL) have been investigated at different temperatures above and below Tg. The results were analyzed using the Cole-Cole representation and lead to the conclusion that this mixture does not exhibit micro-scale heterogeneities. Dielectric constant and dielectric loss master curves were constructed using the stress relaxation shift factors determined previously; the same shift factors could be used for the homopolymers and their blends. Similarities between the dielectric master curves and the stress relaxation master curves of PVC, PMPPL, and their blends, are also discussed.
    Additional Material: 12 Ill.
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  • 64
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    Polymer Engineering and Science 24 (1984), S. 175-184 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An experimental study was carried out to investigate the isothermal and non-isothermal curing kinetics of unsaturated polyester and vinyl ester resins, using differential scanning calorimetry (DSC). Emphasis was put on investigating the effect of low-profile additives on the curing kinetics of the thermo-setting resins. For the study, a general-purpose polyester resin and a vinyl ester resin were used, together with polyvinyl acetate (PVAc) as low-profile additive, benzoyl peroxide as initiator, and N,N-dimethyl aniline as promoter. It has been found that (1) the addition of the low-profile thermoplastic-additive decreases the rate of cure and, also, the final degree of cure of the resins, (2) the total heat of cure generated by isothermal cure is lower than that generated by non-isothermal cure, and (3) the resin/initiator mixture with promoter exhibits two major exotherm peaks during non-isothermal cure, but only a single exotherm peak during isothermal cure.
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  • 65
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    Polymer Engineering and Science 24 (1984), S. 205-210 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A phenomenological model of entanglement networks is developed and applied to deformed glassy polymers. Thermal expansivities and birefringence are analyzed. The model assumes a stable network of entanglements up to draw ratios of about 5. Beyond that range the entanglement structure breaks down to maintain a nearly constant drawing stress. The results are used to determine the ultimate linear expansivities of atactic polystyrene.
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  • 66
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    Polymer Engineering and Science 24 (1984), S. 227-241 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Distortion of bars injection-molded from polystyrene, polypropylene, and glass-fiber-filled polypropylene and subsequently placed in a temperature gradient has been examined. Residual stress distributions have been measured both for the as-molded state and after annealing in a temperature gradient. In the as-molded state all moldings showed the usual residual stress distribution with compressive stresses near the surface and tensile stresses in the interior. In all three materials it was found that tensile stresses could be developed near to the warmer surface on gradient annealing and that tensile stresses still remained at this surface when the bar was cooled and permitted to bend to restore internal equilibrium. It is shown therefore that in addition to the dimensional changes which occur and which may render the molding unserviceable after temperature gradient annealing, another undesirable change takes place, leaving the molding much more susceptible to fracture from a surface flaw. Uniform annealing is found to be much less likely to cause stress reversal and the stresses remain balanced so that distortion is minimal.
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  • 67
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    Polymer Engineering and Science 24 (1984), S. 519-519 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 68
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The mechanical properties of a variety of immiscible binary blends, with and without third component polymeric compatibilizers, are reviewed and qualitatively related to the degree of adhesion between blend components as determined by lap shear testing. Generally, blends comprised of components which adhere well, one to the other, show improved ductility relative to blends of components which do not adhere, Similarly, polymeric compatibilizers are found to be more effective for improving the properties of a binary blend system if they adhere well to both primary components of the immiscible mixture. These results suggest that adhesion between phases in the mixture strongly influences the ultimate properties of the blend. Some evidence is presented which suggests that components which adhere well are partially miscible.
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  • 69
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    Polymer Engineering and Science 24 (1984), S. 598-600 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper presents an overview of the subject of phase separation in polymer blends with an emphasis on the thermodynamic stability criteria for phase stability and the classical thermodynamic and microscopic description of polymer interfaces.
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 71
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    Polymer Engineering and Science 24 (1984), S. 421-427 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The extent of molecular degradation of amorphous polystyrene when subjected to mechanical grinding at cryogenic temperature has been investigated using electron spin resonance, infrared spectroscopy, and viscometry. Essentially identical concentrations of chain ruptures in the degraded samples were found from infrared spectroscopic determinations of molecular end group concentrations and by the changes in the viscosity-average molecular weights. The chain-scission concentration was from two to four times the free-radical concentrations, indicating that free-radical-propagation reactions play a much less dominant role in the degree of molecular damage associated with mechanically induced chain scission in glassy polymers. In addition, experiments were carried out as a function of molecular weight and these indicated a virtual independent behavior with molecular weight.
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  • 72
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    Polymer Engineering and Science 24 (1984), S. 79-86 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An abbreviated review of the current state of knowledge of polymer interfacial phenomena is given. Classical thermodynamics treats the interfacial zone (the interphase) as a “black box” and yields rigorous relationships among interfacial quantities. A recent reformulation of interphase thermodynamics, which eliminates the use of a Gibbs dividing surface, is shown to be an invaluable tool for investigating interfacial properties. Microscopic theories, such as the gradient theory, yield more details about what is in the black box, but the information is only approximate. The gradient theory has been used to: (1) relate the surface tension of a polymer liquid to its isothermal compressibility, (2) develop a quantitative theory of polymer liquid surface tension, and (3) determine the interfacial tension between two immiscible polymer liquids. The gradient theory will be shown to be in harmony with the microscopic theory of Helfand and co-workers although the latter treats polymer interfaces from a completely different point of view.
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  • 73
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    Polymer Engineering and Science 24 (1984), S. 698-706 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Thermosetting materials have found widespread use over a broad spectrum of engineering applications due to their intrinsic mechanical strength, thermal and dimensional stability, and other unique properties. Consideration is given to those aspects of reaction kinetics, rheology, fluid mechanics, and heat transfer which are of relevance for the mathematical modeling of reactive polymer processing. Particular emphasis is given to the characterization of reaction kinetics under non-isothermal conditions, the effect of fillers or reinforcing agents on the heat transfer and kinetic behavior, and the complex nature of the interactions brought about by the reactivity of these systems. In addition, the current status of the mathematical simulation of reactive polymer processing is briefly reviewed.
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  • 74
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    Polymer Engineering and Science 24 (1984), S. 843-843 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 75
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    Polymer Engineering and Science 24 (1984), S. 921-929 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The evolution of poly(methyl methacrylate) (PMMA) during physical aging at 90°C is followed by torsional microcreep tests. On the aged specimen a longitudinal stress is applied which induces a strain of 5 percent after 30 days of creep. The torsional microcreep tests are performed during the longitudinal creep in order to compare the structure evolution of PMMA caused by straining with its evolution measured during aging. The microcreep, for the first 800s, follows a reversible logarithmic law. In this stage the mobile defects achieve their activated form which is perfectly reversible when unloaded. The physical aging reduces this logarithmic part of microcreep. This is due to the decrease of either the number or the volume of the mobile defects. Beyond a critical elongation ∊ = 1 percent, the longitudinal straining has just the opposite influence, i.e., the logarithmic part of microcreep increases. This critical elongation ∊ = 1 percent corresponds to the beginning of the steady state longitudinal creep. The transient that precedes this steady state has no detectable influence on the structure of the specimen.
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  • 76
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    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 77
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    Polymer Engineering and Science 24 (1984), S. 345-349 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Small angle X-ray scattering (SAXS) has been used to evaluate the size and concentration of voids in poly(N,N′-bis-(phenoxyphenyl)pyromellitimide), PMDA-ODA. Analysis of the angular dependence of the scattering indicates the presence of voids ranging from 50 to 150 Å in radius. Integrated SAXS demonstrated that the volume fraction of voids was 7 × 10-4. These results were supported by measurements of the attenuation factor as a function of the sample thickness.
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  • 78
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    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 79
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    Polymer Engineering and Science 24 (1984), S. 1087-1103 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The response of glass-forming systems to isobaric three-step thermal cycles involving cooling, isothermal annealing, and subsequent reheating has been investigated comprehensively using numerous combinations of the experimental and material parameters. The latter include the retardation spectrum or response function and the parameter x which determines the relative contributions of temperature and structure to the retardation times. The results show that, on heating, multiparameter systems can display three kinds of peak in the expansion coefficient α or the heat capacity Cp originating from the interactions of the elementary retardation processes with the thermal history of the glass. The conditions under which these peaks occur, their shifts with x, and the experimental variables have been investigated in detail. In particular, it has been shown that for a thoroughly stabilized glass reheated rapidly, the temperature at which the main peak occurs is strongly dependent on the experimental variables and on x, and that this dependence can lead to an estimate of the value of x. For poorly stabilized glasses reheated slowly, on the other hand, the main peak apparently vanishes and allows an upper peak to appear, which is small and insensitive to x and the experimental variables. Intermediate situations in which the main and the upper peaks occur separately give rise to a range of effects which may become quite complicated as the two peaks approach each other. The occurrence of such multiple peaks, which has usually been overlooked or misinterpreted in the past, is discussed and explained in detail and is compared with some experimental observations reported in the literature.
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  • 80
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    Polymer Engineering and Science 24 (1984), S. 1130-1137 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The relationship of valence-coordinate deformation to the temperature dependence of some infrared peak-absorption frequencies in Poly(vinyl chloride) (PVC) and polystyrene (PS) is stated. A skeletal band and a CH2 rocking band in PVC and a ring-mode band in PS were studied in two kinds of experiments: steady heating and cooling of a quenched (nonequilibrium, glassy) sample through its glass-transition temperature, Tg, and long-term annealing of quenched samples below Tg, followed by steady heating and cooling. The results, a slope discontinuity, ΔM, in the v(T) relation at Tg and a frequency shift, Δviso, during isothermal annealing below Tg, are analyzed in two theoretical approaches. Interchain and intrachain contributions to the observed frequency shifts are expected to occur with a differing relative significance in different kinds of molecular vibrations, leading to one possible method of distinguishing valence-coordinate deformation (chain strain) from other effects.
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  • 81
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    Polymer Engineering and Science 24 (1984), S. 117-126 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An attempt was made to melt incorporate ultra high molecular weight polyethylene, UHMWPE, into medium density polyethylene, MDPE. The behavior of the mixtures, containing up to 6 wt percent of UHMWPE, was examined using mechanical and rheological testing. The mechanical test results were found to contain large experimental errors, which makes interpretation very difficult. On the other hand, melt rheology studies, using dynamic and extensional deformations, gave direct insight into the extent and effect of blending. Degradation during the processing was evaluated by size exclusion chromatography. The degree of dispersion of the UHMWPE was examined under the optical microscope.
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  • 82
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    Polymer Engineering and Science 24 (1984), S. 112-116 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This note describes the application of infrared spectroscopy to determine the proportion of ester groups of poly(∊-caprolac-tone) which are involved in specific interactions with the hydroxyl groups of the poly(2-hydroxypropyl ether of bisphenol A) (Phenoxy, Union Carbide) in a series of miscible blends of the two polymers, Even with a fifteen-fold excess of hydroxyl groups, only about 50 percent of the ester groups of poly(∊-caprolactone) are hydrogen-bonded, presumably reflecting steric restrictions to the ester-hydroxyl interactions. Partially miscible blends of these two polymers may also be prepared by a suitable choice of casting solvent, and infrared spectroscopy may then be used to follow the kinetics of miscibility when the partially miscible blend is heated.
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  • 83
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    Polymer Engineering and Science 24 (1984), S. 153-162 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The transport of small molecules (gases) in incompatible polymer blends, semi-crystalline polymers, and filled polymer systems is usually examined in terms of transient sorption and permeation experiments which yield effective values of diffusivity and permeability. From a modeling standpoint these complex systems can be regarded as composites with complex morphology whereas the gas can be considered as a molecular probe of the morphology and especially its connectedness. In this paper we present a brief review of transport descriptions in prototype ordered and disordered systems with special emphasis on simulation of transient measurements. The simulations presented are selected in such a way as to aid in the interpretation of experimental results obtained by sorption and permeation and in the construction and evaluation of morphologies with desired effective transport properties.
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  • 84
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    Polymer Engineering and Science 24 (1984), S. 185-193 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The tranesterification step of the polyethylene terephthalate (PET) formation consists of several side reactions in addition to the main ester interchange, transesterification, and polycondensation reactions. The side reactions considered in this work are acid end group, acetaldehyde, diethylene glycol, water, and vinyl end group formations. The objective function of the batch esterinterchange reactor is assumed to consist of maximizing the conversion and simultaneously minimizing the formation of side products. The control vector iteration procedure has been used to optimize the esterinterchange reactor and the temperature-time profile that gives the best performance has been found. It is found that the reactor should be operated at a high temperature initially to obtain high conversion of dimethyl terephthalate (DMT) first, but then it should be lowered to reduce the formation of side products.
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  • 85
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    Polymer Engineering and Science 24 (1984), S. 211-217 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Internal cracking and microvoids are shown to form during room temperature storage of polycarbonate samples that have previously been exposed to boiling water. These microcracks or microvoids are actually disc-shaped pockets filled with water. This formation occurs due to the creation of water super-saturation conditions by cooling water-saturated specimens from 100°C to room temperature. As a result, water phase-separation, clustering, and microvoiding result and lead to deterioration of the mechanical properties. Visual healing of the microcracks is also sometimes observed at room temperature, especially under a dry atmosphere. Water from the water-filled pockets diffuses through the polycarbonate matrix to the external dry environment; the very thin emptied pockets then close and visually heal. This paper provides experimental data for the microvoiding process and clarifies the special mechanism of cracking/healing in polycarbonate samples.
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  • 86
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    Polymer Engineering and Science 24 (1984) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 87
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    Polymer Engineering and Science 24 (1984), S. 252-258 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The performance of liquid rubbers as low-temperature plastcizers for bitumen was evaluated by the torsional braid technique developed by Gillham. The low-temperature dynamic mechanical properties of bitumen-liquid rubber mixtures were measured from ambient to -100°C and compared with the corresponding fracture behavior using a modified Fraass test. Microscopic observation of the mixture revealed that the liquid rubber was partially soluble in the bitumen at 23°C and at concentrations greater than 10 percent tended to form colloidal dispersions of rubber particles having mean diameters of approximately 10 μm. The loss tangent maxima shifted to lower temperatures and became less pronounced as the concentration of liquid polybutadiene increased. The colloidal rubber dispersion further contributed to the ductility and reduced the brittle temperature of the bitumen at -30°C at 20 percent liquid rubber concentration. The reduction in the brittle temperature of the bitumen is related to the glass-transition temperature of the added rubber, those rubbers having, the lowest glass-transition temperatures being most efficient. Such modifications are necessary to reduce the tendency of asphaltic paving materials to crack in cold climates.
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  • 88
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    Polymer Engineering and Science 24 (1984), S. 1253-1259 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: For free radical oligomerization of styrene, a scheme for calculating the molecular weight distribution and conversion in a continuous-stirred tank reactor (CSTR) train is developed, which also allows the calculation of molecular weight distribution (MWD) for batch reaction. Calculations show that under conventional or near dead-end condition: (1) increasing initial initiator concentration, reaction time and reaction temperature, and decreasing initial monomer concentration cause P̄n and P̄w to decrease and MWD to narrow; (2) increasing initial initiator concentration, reaction time and reaction temperature, and increasing monomer concentration cause monomer conversion to increase; (3) a single CSTR gives a lower rate of oligomer production, but a narrower MWD than does a batch reactor.
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  • 89
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    Polymer Engineering and Science 24 (1984), S. 1270-1276 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The glass-transition temperature of an epoxy resin cured at two different temperatures and plasticized with water and dibutylphthalate has been studied. Both modulus of elasticity and yield stress were measured as a function of temperature to determine the glass-transition temperature. Drying a saturated material appeared to restore the glass-transition temperature to its original value but some broadening of the transition occurred. The behavior of an undercured epoxy when saturated with water could not be predicted by theory. A substantial increase in the transition temperature was observed which may have been caused by the presence of water and an expanded structure.
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  • 90
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    Polymer Engineering and Science 24 (1984), S. 1290-1290 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 91
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    Polymer Engineering and Science 24 (1984), S. 1300-1305 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In a series of publications we reported on melt rheology, morphology, and mechanical properties of the poly(ethylene terephthalate)/poly(amide-6,6) blends (PET/PA). The non-oriented samples had poor interphase bonding resulting in low impact and tensile strengths. To improve these properties the ester-amide interchange reaction was carried out in solution and in melt. In the latter case a Brabender Plastograph was used in the mixing chamber or twin-screw extruder configurations with p-toluenesulfonic acid as a catalyst. The interchange reaction was followed by 400 MHz proton and 13C nuclear magnetic resonance spectroscopy.
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  • 92
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    Polymer Engineering and Science 24 (1984), S. 350-354 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A large number of studies have been devoted in recent years to the miscibility behavior of linear polyesters with chlorinated polymers, including poly(vinyl chloride) (PVC), chlorinated PVC, chlorinated poly(ethylenes), and copolymers of vinylidene chloride (Saran). However, similar studies with aromatic polyesters are lacking. It is the purpose of this paper to compare the properties of blends made of poly(ethylene terephthalate), poly(butylene terephthalate) or poly(hexamethylene terephthalate) and of various chlorinated polymers. It is shown that a high concentration of chlorine atoms is required to achieve miscibility. Moreover, there is a “miscibility window” in terms of the carbonyl concentration of polyesters, immiscibility being found for carbonyl concentrations outside this window, A similar behavior was observed before for linear polyester/chlorinated polymer blends and for polyester/polycarbonate blends. Solid state small-angle light scattering experiments were also conducted to follow the morphology of the blends as a function of composition. Spherulites were found but their size vary with composition.
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  • 93
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    Polymer Engineering and Science 24 (1984), S. 750-760 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Some recent observations on shear bands in polymers are reviewed. These include intrinsic properties such as the mechanism of formation, the intersection of shear bands, the rate of propagation with and without obstacles, recovery of shear strain by annealing, and the stored energy in shear bands. Mechanical responses include the shear yielding criteria, reverse shear behavior and the Bauschinger effect, and the fracture of and at shear bands. Environmental effects include methanol transport in shear bands and in deformed poly(methvl methacrylate) in the region of mixed Fickian and case II behavior and methanol crazing of a shear banded material.
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  • 94
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    Polymer Engineering and Science 24 (1984), S. 786-797 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The performance of styrene-acrylonitrile copolymers under alternating stresses has been examined. Information has been obtained concerning the influence of acrylonitrile content and of molecular weight on thermal effects due to hysteresis, on cyclic lifetime to craze initiation, on average cycles to fracture, and on fatigue fracture surface morphology. The influence of an elastomeric second phase has been determined by comparing fatigue performance under comparable conditions of both styrene-acrylonitrile (SAN) and acrylonitrile-butadiene-styrene (ABS). The stress concentrating effects of the rubber particles cause earlier initiation of fatigue-induced damage and lower fatigue fracture resistance. The fatigue-induced specimen temperature rise is greater in ABS than SAN and it increases linearly with test frequency and as the square of the stress amplitude. The fracture surface morphology of ABS, which differs from that of unmodified SAN and also from that of rubber modified polystyrene, is discussed.
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  • 95
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    Polymer Engineering and Science 24 (1984), S. 814-819 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Plane elasticity theory is utilized to obtain expressions for the stress and displacement fields at the tip of a craze containing a crack. The craze is modeled as a very thin elliptical inclusion with different elastic properties from hat of the surrounding bulk polymer. Problem is solved by superimposing the solution of a crack problem onto the solution for a uniformly loaded homogeneous craze. Invoking stress free boundary conditions on the crack surface provides a singular integral equation of Hilbert type with a unique solution. Contour lines of constant hydrostatic stress and constant maximum shear stress around the craze tip are shown graphically. These two stress combinations have played prominent roles in a number of proposed craze growth criteria. Results show that even for relatively long cracks within the craze, very little stress enhancement at the craze tip occurs. Only as the crack tip approaches the craze tip does the enhancement become significant, tending to drive the craze region ahead of the crack.
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  • 96
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    Polymer Engineering and Science 24 (1984), S. 844-850 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Three types of pressure dependent deformation processes have been observed for the short glass fiber reinforced composites of poly(vinyl chloride) (PVC). A unique deformation behavior, observed for the first time, features a sharp drop in stress followed by shear yielding in the matrix. Competitive pressure dependent failure processes in the composites are strongly affected by “debonding” at the fiber-matrix interface. A new general pressure dependent yield criterion for PVC and its composites was elucidated.
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  • 97
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    Polymer Engineering and Science 24 (1984), S. 877-885 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The mechanical behavior of chlorinated polyethylene (CPE)-modified poly(vinyl chloride) (PVC) has been determined. The nature of the irreversible deformation processes which are responsible for mechanical energy absorption has been investigated by optical and electron microscopic techniques. Addition of CPE results in a decrease in the shear band initiation stress and an increase in void density and stability. The crazing to shear banding transition is observed at a blend composition between 2 and 7 percent CPE at the strain rate employed. It has been established that voiding occurs in the CPE rubber phase. Voiding accounts for at least part of the increased energy absorption of the blend. The stability of the voids to coalescence and fracture is attributed to strong adherence of the CPE to the primary PVC particles.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 535-540 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Tensile, tensile impact, compact tension, and fatigue tests were carried out on ABS (acrylonitrile-butadiene-styrene), HIPS (high impact polystyrene), and toughened PMMA (poly(methyl methacrylate)). Dumbbell specimens machined from test pieces were then subjected to sinusoidal tension-compression cycling at low stress amplitudes. The HIPS specimens produced asymmetrical hysteresis loops characteristic of multiple crazing, whereas PMMA gave more symmetrical, regularly shaped, loops. The behavior of the ABS polymers varied with loading history. It was concluded that the hysteresis test provides a useful additional technique for studying deformation mechanisms, especially under conditions that do not readily permit volumetric measurements.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 587-597 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In the past decade, polymer blend technology has achieved an important position in the field of polymer science. With increased academic and industrial research interest, the application of polymer blend technology to commercial utility has grown significantly. This review on the applications of polymer blends will cover the major commercial blends in the categories of styrene-based polymer blends, poly(vinyl chloride) blends, polyacrylate blends, polyester and polycarbonate blends, polyolefin blends, elastomer blends, polyelectrolyte complexes, and interpenetrating polymer networks. New developments in polymer blend applications will be discussed in more detail. These systems include linear low-density polyethylene blends with either low- or high-density polyethylene, styrenemaleic anhydride terpolymer/ABS (acrylonitrile-butadiene-styrene) blends, polycarbonate/poly(butylene tetephthalate) blends, new PPO/polystyrene blends, and tetramethyl bisphenol A polycarbonate/impact polystyrene blends. Areas for future research to enhance the potential for polymer blend applications will be presented. The need for improved methods for predicting miscibility in polymer blends is discussed. Weldline strength is a major property deficiency of two-phase systems (even those with mechanical compatibility), and future research effort appears warranted to resolve this deficiency. The use of polymeric compatibilization additives to polymer blends has shown promise as a method to improve mechanical compatibility in phase-separated blends, and will be expected to be the subject of future research programs. Finally, the reuse of polymer scrap is discussed as a future application area for polymer blends. Unique applications recently proposed for polymer blends include immobilization of enzymes, permselective membranes, reverse osmosis membranes, selective ion-exchange systems, and medical applications using polyelectrolyte complexes.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 974-979 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The simultaneous production of polyurethane (PUR) and polymethyl methacrylate (PMMA), starting from a mixture of polyol, polyisocyanate, and vinyl monomer, results in 2-phase polymer alloys. A simultaneous crosslinking of the PMMA is unable to prevent phase separation during the curing reaction; interpenetrating polymer network (IPN) structures were not found, Grafting the PMMA onto the PUR through the incorporation of 2-hydroxyethylacrylate resulted in single-phase systems. Various material combinations did not show, with a relatively high PMMA content, any poorer properties than the straight PUR. A major advantage of incorporating low-viscosity vinyl monomers lies in the fact that high-viscosity polyurethane starting components that are otherwise difficult or impossible to process can be processed here without problem.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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