Degradation and fragmentation behavior of polypropylene and polystyrene in water

The polystyrene (PS) retrieved from the beach exhibited no change in surface texture. In contrast to it, the retrieved polypropylene (PP) had a rumpled surface texture. Highly reactive sulfate radical generated by K2S2O8 was employed as degradation initiator of PP and PS, and their degradation behavior was studied in water. The PS carbonyl index value gradually went up down, and its molecular weight (MW) curve discontinuously shifted to a lower MW with the increase of the degradation time unlike the PP. It was found that the PP microplastic production rate was approximately three time higher than the PS from weight ratio dependence on degradation time. The higher microplastic production rate of PP arose from its crystallizability. The voids were produced by change in specific volume occurring by chemi-crystallization and then provoked the cracks leading to quick fragmentation. The SEM photographs suggested that the PP microplastic size facilely reached nm order by the cracking around lamella

Direct Observation of Microphase-separated Structure of Polyurethane by Temperature Dependent Atomic Force Microscopy

Nagasaki Symposium on Nano-Dynamics 2008 (NSND2008) 平成20年1月29日(火)於長崎大学 Poster Presentatio

Difference in polypropylene fragmentation mechanism between marine and terrestrial regions

Two kinds of marine polypropylene (M1-PP and M2-PP) and one land PP (L-PP) samples were collected from two beaches and land in Japan, respectively, to study the fragmentation mechanisms. Delamination was observed on both M1-PP and M2-PP surfaces. Moreover, there was no delamination but an abrasion patch structure on the surface of L-PP. The delamination was studied using an advanced oxidation process-degraded PP as the marine PP model. The number and shape of cracks varied with an increase in degradation time. The fluctuations in the values and ratios of the carbonyl index as well as the weight change ratio were due to repeated oxidation and delamination. We found that the delamination behavior depends on the oxidation state. Poly(oxyethylene)8 octylphenyl ether (POE8) surfactant treatment caused the delamination to speed up, which is a typical characteristic of polyolefin environmental stress cracking (ESC). These results reveal that delamination is based on ESC

Chain and mirophase-separated structures of ultrathin polyurethane films

Measurements are presented how chain and microphase-separated structures of ultrathin polyurethane (PU) films are controlled by the thickness. The film thickness is varied by a solution concentration for spin coating. The systems are PUs prepared from commercial raw materials. Fourier-transform infrared spectroscopic measurement revealed that the degree of hydrogen bonding among hard segment chains decreased and increased with decreasing film thickness for strong and weak microphase separation systems, respectively. The microphase-separated structure, which is formed from hard segment domains and a surrounding soft segment matrix, were observed by atomic force microscopy. The size of hard segment domains decreased with decreasing film thickness, and possibility of specific orientation of the hard segment chains was exhibited for both systems. These results are due to decreasing space for the formation of the microphase-separated structure.IUMRS-ICA 2008 Symposium Sessions X and Y. Soft Matter Science, 9-13 December, Nagoya, Japa

Rapid oxidative fragmentation of polypropylene with pH control in seawater for preparation of realistic reference microplastics

Various tiny plastic particles were retrieved from the sea and studied using scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis to prepare realistic reference microplastics (MP). Most of the MP exhibited a diameter of < 20 × 10−6 m and 0.1–0.2 molar ratios of oxygen to carbon atoms (O/C), indicating that they primarily comprised polyethylene (PE), polypropylene (PP), and polystyrene (PS). It took a long time to reproduce such O/C ratios in standard laboratory weathering methods. For example, degrading of 30 × 30 × 0.060 mm PP film required 75 days for the 0.1 ratio, even with an advanced oxidation process (AOP) using a sulfate radical anion (SO4·−) initiator in distilled water at 65 °C. However, seawater drastically improved the PP degradation performance of AOP under a weak acid condition to achieve the 0.1 ratio of PP film in only 15 days. The combination of seawater and the SO4·− initiator accelerated the degradation process and showed that the MP’s size could be controlled according to the degradation time

Molecular Mobility of Soft Segment of Polyurethane Elastomers under Elongation

Abstract. In this study, we investigated molecular mobility of a soft segment in the poly(oxypropylene) glycol (PPG), 4,4\u27-diphenylmethane diisocyanate (MDI) and 1,4-butane diol (BD)-based polyurethane elastomers (PUE) with and without elongation by dynamic viscoelastic property measurement and pulse nuclear magnetic resonance (NMR) measurement. The peak position of the loss tangent (tand) curves shifted to the lower temperature region with increasing elongation. In the pulse NMR measurement, the long spin-spin relaxation time {T2) component appeared at -18.0 (e = 0) and -26.0 °C (e =1.5), respectively, with increasing temperature. Since this temperature seems to be related to the glass transition temperature (Jg) of the soft segment in the PUE, it is likely to consider that the Tg decreased with increasing strain. These results might be attributed that the size of cooperative motion during the glass transition decrease due to the orientation of the soft segment, and the soft segment phase approach to a pure phase on account of the extraction of the hard segment from the soft segment phase.THE XV INTERNATIONAL CONGRESS ON RHEOLOGY: The Society of Rheology 80th Annual Meeting : Monterey (California), 3?8 August 200

Porous In2O3 powders prepared by ultrasonic-spray pyrolysis as a NO2-sensing material: Utilization of polymethylmethacrylate microspheres synthesized by ultrasonic-assisted emulsion polymerization as a template

NO2-sensing properties of porous In2O3 (pr-In2O3) powders prepared by ultrasonic-spray pyrolysis employing polymethylmethacrylate (PMMA) microspheres as a template has been investigated in this study. The PMMA microspheres were synthesized in water by ultrasonic-assisted emulsion polymerization employing methyl methacrylate monomer, sodium lauryl sulfate as a surfactant and ammonium persulfate as an initiator. The PMMA microspheres synthesized was quite uniform and the particle size was ca. 60.2 nm (measured by dynamic light scattering). The microstructure of pr-In2O3 powders prepared was largely dependent on the kind of In2O3 sources. The pr-In2O3 which was prepared from In(NO3)3 as an In 2O3 source (pr-In2O3(N)) consisted of submicron-sized spherical particles with welldeveloped spherical mesopores (several tens of nanometers in pore diameter) and each oxide wall among pores was constructed with meso-sized In2O3 particles connected continuously. On the other hand, the pr-In2O3 which was prepared from InCl3 as an In2O3 source (pr-In2 O3(Cl)) was composed of a large number of dispersed meso-sized particles and a few submicron-sized dense spherical particles. In contrast, the morphology of conventional In2O3 powder (c-In 2O3) prepared by ultrasonic-spray pyrolysis of PMMAfree In(NO3)3 aqueous solution as a reference was relatively dense and roughly spherical with a diameter of ca. 100-700 nm. The responses to 1.0 and 10ppm NO2 of pr-In2O3 sensors in air were much larger than those of a c-In2O3(N) sensor in the temperature range of less than 250°C and 300°C, respectively. In addition, the response and recovery speeds of both the pr-In2O 3 sensors were much faster than those of the c-In2O 3(N) sensor, because of the well-developed porous structure of the pr-In2O3 sensors

Hydrolysis of aromatic polyurethane in water under high pressure of CO2

We have demonstrated a hydrolysis reaction of polyurethane (PU) under high pressure of carbon dioxide (CO2) in water. We employed the PU sample, poly(methylene bis-(1,4-phenylene)hexamethylene dicarbamate), denoted as M-PU, which was synthesized from 4,4′-diphenyl methane diisocyanate and 1,4-butane diol (BD). The optimum hydrolysis reaction condition was 190 °C under CO2 pressures over 4.1 MPa in water medium, and 93% hydrolysis of M-PU was achieved. After the reaction, the water-soluble parts were obtained, and isolated by column chromatography. The isolated products were 4,4′-methylenedianiline (MDA) and 1,4-butane diol (BD), which were components of repeating unit of M-PU. In addition, the hydrolysis reaction gave no byproduct. This hydrolysis under high pressure of CO2 with water is a reaction by which M-PU is selectively hydrolyzed into MDA and BD by cleaving urethane linkage. Moreover, the resulting hydrolyzed products were easily obtained by evaporation of aqueous layer after the reaction, indicating an efficient chemical recycling of PU was achieved