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Journal Article
JANETTE RUTTERFORD, DAVID R. GREEN, JOSEPHINE MALTBY and ALASTAIR OWENS
Vol. 64, No. 1 (FEBRUARY 2011), pp. 157-187
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Stable URL: https://www.jstor.org/stable/27919486
Page Count: 31

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The Economic History Review
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publishes articles based on original research on all aspects of economic and social history. is edited on behalf of the Economic History Society by leading scholars. It has been published since 1927 and is one of the world's leading journals in the field. welcomes contributions based on the full range of methodological approaches used by economic and social historians and is pleased to publish high quality research on the economic and social history of any area of the world. The emphasis is on broad coverage of themes of economic and social change, including their intellectual, political and cultural implications. In addition to regular papers, some issues contain contributions to a series of 'Surveys and Speculations' which are more reflective survey articles. For many years past a comprehensive annual list of publications on the economic and social history of Great Britain and Ireland has been published. Each issue also contains a substantial number of book reviews. JSTOR provides a digital archive of the print version of . The electronic version of is available at http://www.interscience.wiley.com . Authorized users may be able to access the full text articles at this site.

Coverage: 1927-2012 (Vol. 1, No. 1 - Vol. 65, No. 4)
Moving Wall:

The "moving wall" represents the time period between the last issue available in JSTOR and the most recently published issue of a journal. Moving walls are generally represented in years. In rare instances, a publisher has elected to have a "zero" moving wall, so their current issues are available in JSTOR shortly after publication. Note: In calculating the moving wall, the current year is not counted. For example, if the current year is 2008 and a journal has a 5 year moving wall, articles from the year 2002 are available.

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Figure 2: DRIFT spectra of the nanoparticle samples NP-RA, NP-MMA and NP-PMMA-3.

Figure 2:

Figure 2: DRIFT spectra of the nanoparticle samples NP-RA, NP-MMA and NP-PMMA-3.

Jump to Figure 2

Three different events can lead to the copolymerization and attachment of the PMMA chains to NP-MMA: i) initiation occurs on the NP-MMA, resulting in PMMA chain(s) growing from the surface of the NP-MMA (blue circle in hook amp; loop sneakers Black Pierre Hardy Popular Cheap Price Best Seller Online jz3BpZ198
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); iii) growing PMMA chain copolymerizes with methacrylate unit(s) on the surface of more than one NP-MMA particle, resulting in the formation of covalent links between the NP-MMA surfaces (green circle in Scheme1 ).

Of the three events, the last one is the most dependent on the concentration of NP-MMA and can even lead to cross-linking. The relative occurrence of this event should have a major influence on the colloidal stability of the NP-PMMA suspension and the hydrodynamic size of the NP-PMMA. The gel properties of the suspension of the NP-PMMA-3, where the concentration of the NP-MMA was the highest, indicate the relatively high content of the PMMA chains connecting several neighboring nanoparticles.

The size of the NP-PMMA-3 nanoparticles and the free PMMA chains were probed using dynamic light scattering (DLS). Two distinct populations were found in the suspension of nanoparticles denoted as NP-PMMA-3 ( Figure3 ).

Figure 3: Number-weighted hydrodynamic diameter size-distribution function of the NP-RA and NP-PMMA-3 nanoparticle samples.

Figure 3:

Figure 3: Number-weighted hydrodynamic diameter size-distribution function of the NP-RA and NP-PMMA-3 nanopar...

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The distribution function for the smaller diameter region was extremely narrow, with the mode at 2 nm. The distribution function for the larger diameter region is strongly skewed and the median, having the value of 45 nm, is a better estimate of the “average” hydrodynamic diameter than the mean or mode. The distribution functions were well separated; therefore, we can conclude that the one centered at 2 nm described the hydrodynamic size of the free polymer chains, and the other one, the NP-PMMA nanoparticles. Additionally, the sPMMA sample was measured. In this case the signal was weak so the autocorrelation function was acquired at a low angle, i.e., at a small scattering vector that makes it possible to probe the fast dynamics of small polymer chains. The resulting distribution function of the hydrodynamic size of the polymer chains was centered at approximately 4 ± 2 nm. The large error is due to the weak signal. On the other hand, in the NP-PMMA-3 sample, the scattering from the nanoparticles overwhelmed the scattering from the small polymer chains, also making an estimation of their size less reliable. We believe that the hydrodynamic diameter of the free PMMA chains being between 1 nm and 4 nm is a valid assumption. The distribution function of the NP-RA nanoparticles is less skewed with a median of 30 nm. The number-weighted average size and the median of the nanoparticles NP-RA determined from the TEM images were 11.0 ± 2.3 nm and 10 nm, respectively ( Supporting Information File1 , Figure S6). Considering the fact that the suspension of NP-RA was colloidal, the relatively large hydrodynamic size is related to the exceedingly good solvation of the RA chains by toluene. The increase in the hydrodynamic size from 30 nm to 45 nm during the polymerization is clearly related to the copolymerization of the NP-MMA and MMA. The relatively large hydrodynamic size and the increased skewness of the hydrodynamic size-distribution function of the NP-PMMA-3 suggest that some NPs were linked together; however, the number of the individual NPs linked together is quite low. This indicates that branched structures with NPs acting as the branching points were most likely formed instead of a fully cross-linked gel. The fact that the hydrodynamic size of the NP-PMMA nanoparticles was still large in the diluted sample was a further proof that the polymer chains were strongly attached, not only adsorbed onto the surface of the nanoparticles.

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