ESTIMATION FOR NONNEGATIVE AUTOREGRESSIVE PROCESSES WITH AN UNKNOWN LOCATION PARAMETER

Abstract. Consider an AR(1) process given by X ^t=γ+ø X _t+ Z _t≥ 1. where 0 ≤γ, 0 ≤ø 1 are unknown parameters and the innovations Z _t, ≥ 1, are independently and identically distributed positive random variables. We propose estimates of (γø) which are obtained as the solution to a linear programming problem and establish their strong consistency. When the Z _ts have the exponential distribution. our estimate becomes the conditional maximum likelihood estimate given X ₀. Under the assumption of regular variation of the innovation distribution at its left and right endpoints (assumed to be 0 and ∝ respectively), we establish asymptotic limit laws for the estimates. Consistent estimators for a class of moving-average processes with heavy-tailed innovation distribution are also presented.     

Saponification kinetic study of mica-acrylonitrile graft copolymers

Kinetics of alkaline hydrolysis of mica-acrylonitrile graft copolymers was studied. The dependence of alkali concentration and the time of hydrolysis on the degree of saponification was determined. Chemical and spectroscopical techniques were used to determine the mechanism of hydrolysis.     

Anionic synthesis of poly(epichlorohydrin-g-styrene) and chemical modification of polyepichlorohydrin

Poly(epichlorohydrin-g-styrene) copolymers, P(ECH-g-S)s, have been prepared in solution by two different methods of coupling polyepichlorohydrin, PECH, with polystyrene, PS, containing a functional end group. In the first method, polystyryl carboxylic acid, PSCOOH, prepared from living polystyrene, was converted to the corresponding potassium salt which was coupled with PECH in dimethyl formamide solution usually at 60°C. In the second method, polystyryl potassium, PS^?K⁺, in tetrahydrofuran solution was end-capped with propylene sulphide to form PSCH₂CH(CH₃)S^?K⁺ which was coupled directly with PECH in tetrahydrofuran at 40°C. Grafting by the first reaction was relatively slow but occurred without significant adverse side reactions. The grafting by the second reaction was relatively fast, but side reactions occurred resulting in a cleavage of the graft copolymer. The graft copolymers were purified by fractional precipitation and extraction procedures and were characterized by infra-red and ultra-violet spectroscopy, microanalysis, gel permeation chromatography, differential scanning calorimetry, solution viscometry, dynamic mechanical testing, and electron microscopy. Solution properties of the graft copolymers in benzene-carbon tetrachloride and toluene-cyclohexane mixtures were studied. There was evidence of micelle formation in dilute solutions of the mixed solvents and microphase separation of components in the solid state. Nucleophilic substitution of chlorine atoms in PECH by phenyl acetate (C₆H₅ CH₂COO-) and thiophenoxide (C₆H₅S-) groups was performed.     

Inhibition by 5-(tetradecyloxy)-2-furoic acid of fatty acid and cholesterol synthesis in isolated rat hepatocytes

Fatty acid and cholesterol synthesis in isolated rat hepatocytes were strongly inhibited by 5-(tetradecyloxy)-2-furoic acid. With either³H₂O or [2-¹⁴C]acetate as the labeled precursor, the concentrations of inhibitor causing 50% decrease in fatty acid and cholesterol synthesis were, respectively, <0.005 mM and 0.020 mM. At 0.1 mM inhibitor, citrate concentration in cells from fed rats was increased by 75%; lactate and pyruvate concentrations were decreased by 30%; ethanol oxidation was decreased by 20%; with cells from starved rats, the mitochondrial [NAD⁺]/[NADH] was decreased. Other parameters were unaffected. Both its potency and its specificity indicate that 5-(tetradecyloxy)-2-furoic acid will be useful in studies on the regulation of lipid biosynthesis.     

Highly potent germination inhibitors in aqueous eluate of fruits of Bishop's weed (Ammi majus L.) and avoidance of autoinhibition

The aqueous eluate from fruits ofAmmi majus (Bishop's weed, Umbelliferae) remarkably inhibited germination of adjacent seeds ofAnastatica hierochuntica, lettuce, or tomato but had no effect on intact fruits ofAmmi. Similar inhibition was found in dark or in light, except that seeds ofA. hierochuntica were significantly more inhibited in the dark than in the light. Xanthotoxin was isolated, identified, and found to account for about a sixth of the inhibitory activity of the eluate. After fruits ofAmmi were submerged in a large volume of water for 4 days, the fruits still exuded enough inhibitors to prevent germination ofA. hierochuntica, lettuce, or tomato. Data support also the proposal that the phytotoxins are compartmentalized between the inner and the outer fruit envelopes. The inner layer excludes inhibitors from the embryo and autotoxicity is thus avoided, whereas the outer one ensures a gradual liberation of the phytotoxic compounds. This, as well as the high reactivity of the eluate, the high densities ofAmmi fruits in nature, and their relatively limited annual germination, suggest chemical inhibition of neighboring plant species other thanAmmi. Hence, in addition to their chemical protection against predators of either lower or higher organisms, furanocoumarins in fruits ofAmmi majus may contribute to its success as a weed.     

Mobil Zeolite Catalysts for Monomers

It has been about 20 years since Plank, Rosinski, and Hawthorne reported their spectacular results with metal-modified zeolite cracking catalysts for more efficient production of gasoline [1]. This discovery has saved an estimated 200 million barrels of crude oil each year in the United States alone [2]. In 1972, a patent by Argauer and Landolt described the preparation of a member of a generation of new synthetic zeolites, called ZSM- 5. It was unique because of its high silica/alumina ratio and greatly reduced coking rates for reactions with hydrocarbons by comparison with known low silica zeolites [3]. This material was an early member of a series of over 50 synthetic zeolitic substances prepared in Mobil laboratories.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Mechanical properties and transition temperatures of copolymers of N-n-alkylacrylamides and vinylidene chloride

Mechanical and solution properties, melting transitions, torsional stiffness temperatures, T_f, and selected modulus-temperature curves are presented for copolymers of the N-n-alkylacrylamides with vinylidene chloride. Copolymers were prepared at 60°C across the range of compositions, using as comonomers N-n-butyl-, octyl-, dodecyl- and oleyl-acrylamide, which have amorphous side-chains, and N-n-octadecyl acrylamide and n-octadecyl acrylate whose side-chains are crystalline. The mechanical properties reflected the effect of the decline in backbone crystallinity and the simultaneous development of strong intermolecular interactions in the amorphous stage. Copolymers were stiff or showed brittle failure across the compositional range except when intermolecular forces were reduced (with n-octadrcyl acrylate) and side-chain crystallization eliminated (with N-oleylacrylamide). These systems and the n-dodecylacrylamide copolymers had yield strengths less than brittle strengths and substantial elongations. Backbone crystallinity was eliminated at about 15 mole % amide and side-chain crystallinity vanished at less than 10 mole % of the amide in the N-n-octadecylacrylamide series. No depression in side-chain melting point occurred with dilution by segments of vinylidene chloride. Over-all decline in the flex-temperature was the normal monotonic function of composition except that values increased in magnitude at high vinylidene chloride contents, the effect presumably being caused by the presence of crystallinity. An empirical equation was developed which permitted the calculation of T_f for any N-n-alkylacrylamide composition with any number of carbon atoms in the side-chain, above 3.     

Coal liquefaction in nitrogen compounds

Model compound studies have shown that 1,2,3,4-tetrahydroquinoline is an exceptionally good coal solvent. In the pure compound, subbituminous coal conversion to THF-soluble products approaches 100% under relatively mild reaction conditions. The effectiveness of tetrahydroquinoline for coal conversion appears to be related to its concentration relative to coal. The unique behaviour of tetrahydroquinoline is ascribed to its being a highly active H-donor; the fact that it is regenerable under reaction conditions by the reaction of hydrogen and quinoline; and that its polarity allows penetration of the coal structure and aids in dispersion of the dissolved coal. It has been found that, during reaction with coal, tetrahydroquinoline and other nitrogen compounds undergo extensive condensation reactions which result in an increase in the nitrogen content of the high boiling and non-distillable liquefaction products.     

Effect of theθ-α-Al2O3 transformation on the oxidation behavior ofβ-NiAl + Zr

Isothermal oxidation of NiAl + Zr has been performed over the temperature range of 800–1200°C and studied by TGA, XRD, and SEM. A discontinuous decrease in growth rate of two orders of magnitude was observed at 1000° C due to the formation of -Al₂O₃ from -Al₂O₃. This transformation also resulted in a dramatic change in the surface morphology of the scales, as a whisker topography was changed into a weblike network of oxide ridges and radial transformation cracks. It is believed that the ridges are evidence for a shortcircuit outward aluminum diffusion growth mechanism that has been documented in a number of¹⁸O tracer studies.