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Impact of solvent quality and polyme...

DiNoia, Todd Peter.

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Impact of solvent quality and polymer architecture on polymer-supercritical fluid solutions: Phase behavior and small-angle neutron scattering investigations .

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Impact of solvent quality and polymer architecture on polymer-supercritical fluid solutions: Phase behavior and small-angle neutron scattering investigations ./
作者:	DiNoia, Todd Peter.
面頁冊數:	180 p.
附註:	Source: Dissertation Abstracts International, Volume: 61-03, Section: B, page: 1521.
Contained By:	Dissertation Abstracts International61-03B.
標題:	Engineering, Chemical. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9964085
ISBN:	9780599683341

Impact of solvent quality and polymer architecture on polymer-supercritical fluid solutions: Phase behavior and small-angle neutron scattering investigations .
DiNoia, Todd Peter.

Impact of solvent quality and polymer architecture on polymer-supercritical fluid solutions: Phase behavior and small-angle neutron scattering investigations . - 180 p.

Source: Dissertation Abstracts International, Volume: 61-03, Section: B, page: 1521.

Thesis (Ph.D.)--The Johns Hopkins University, 2000.

The impact of solvent quality and polymer architecture on polymer-supercritical fluid (SCF) solution behavior is studied with a combination of phase behavior and small-angle neutron scattering experiments (SANS). Phase behavior measurements provide a macroscopic description of the underlying physics and chemistry that dictate the location of phase boundaries in pressure-temperature space. SANS measurements provide a microscopic description of the solution structure and polymer conformational properties relative to the macroscopic phase boundaries.

ISBN: 9780599683341Subjects--Topical Terms:

1018531
Engineering, Chemical.

Impact of solvent quality and polymer architecture on polymer-supercritical fluid solutions: Phase behavior and small-angle neutron scattering investigations .
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500 $a Co-Advisers: Mark A. McHugh; John H. van Zanten.
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520 $a The impact of solvent quality and polymer architecture on polymer-supercritical fluid (SCF) solution behavior is studied with a combination of phase behavior and small-angle neutron scattering experiments (SANS). Phase behavior measurements provide a macroscopic description of the underlying physics and chemistry that dictate the location of phase boundaries in pressure-temperature space. SANS measurements provide a microscopic description of the solution structure and polymer conformational properties relative to the macroscopic phase boundaries.
520 $a Phase behavior data for pressures up to 3000 bar and temperatures up to 300°C are presented for poly(olefins), poly(acrylates), poly(methacrylates), poly(vinyl acetate), poly(acrylic acid), copolymers containing both nonpolar olefin and polar acrylate segments, and fluorinated polymers and copolymers containing tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, and trifluoromethyl-difluoro-dioxole segments in supercritical CO2 and halogenated SCF solvents. CO2 is a weak supercritical fluid that cannot dissolve nonpolar polymers and exhibits temperature-sensitive characteristics found in polar solvents. Polymer solubility in CO2 is enhanced by incorporating polar or fluorinated segments in the chain backbone or branching groups. Dramatic shifts in the cloud-point curves are observed for changes in polymer architecture since polymer free volume plays an important role in SCF solubility. CO2 also has solvent characteristics similar to halogenated solvents for dissolving fluorinated polymers. A case study on the life cycle of propellant, explosive, and pyrotechnic (PEP) formulation shows that PEP binder polymers can be processed in environmentally conscious solvents like CO2.
520 $a SANS experiments on polymer-SCF solutions are accomplished with the design of a unique high-pressure scattering cell. Solutions are probed using the high concentration isotopic labeling technique at the mixture-critical concentration to determine the variation in intra- and intermolecular correlations on approach to the phase boundary with isothermal changes in pressure. SANS scattering data is presented for pressure up to 2,500 bar and temperatures to 150°C for a poly(ethylene-co-butene) (PEB) copolymer in supercritical ethane, an ethane plus pentane mixture, liquid pentane, and supercritical dimethyl ether (DME). SANS results show that intermolecular correlations, given by the correlation length, xi, change dramatically as the phase boundary is approached and are much greater in SCF ethane and DME compared to liquid pentane. Intramolecular correlations, defined by the radius of gyration, Rg, do not deviate from the unperturbed theta/melt value on approach to the phase boundary in both SCF and liquid solutions due to screening effects from overlapping chains. However, SANS data for PEB in DME show that intramolecular correlations on length scales proportional to a few polymer segments change significantly on approach to the phase boundary. The observed changes in local conformational properties of the polymer, such as the persistence length, result from variations in solvent quality and excluded volume interactions. Challenges remain to model SANS data with single chain scattering functions that appropriately account for the effects of excluded volume and local conformational properties of polymers in SCF solutions.
590 $a School code: 0098.
650 4 $a Engineering, Chemical. $3 1018531
650 4 $a Chemistry, Polymer. $3 1018428
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