DOI: 10.1063/1.2747596. Vibrational and configurational heat capacity of poly(vinyl acetate) from dynamic measurements

Vibrational and configurational heat capacity of poly(vinyl acetate) from dynamic measurements

10.1063/1.2747596

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The complex heat capacity Cp* of poly(vinyl acetate) has been measured at 20.95mrad∕s modulation frequency during the cooling as well as on heating at 24, 8, and 2K∕h and during cooling at 0.5K∕h. The study is complemented with (the rate-dependent) Cp,app measured during cooling and heating at 60, 24, and 8K∕h. At low temperatures, the real component of Cp* yields the unrelaxed Cp or Cp,vib, the vibrational part of Cp. It is found to be indistinguishable from Cp,glass and lies on a line extrapolated to its equilibrium melt’s temperature. At T near Tg,ΔCp(=Cp,melt−Cp,glass) shows no detectable contribution from Cp,vib. The finding conflicts with a modified entropy theory calculation [E. A. DiMarzio and F. Dowell, J. Appl. Phys. 50, 6061 (1979)], which had predicted that ∼27% of ΔCp of poly(vinyl acetate) at T near Tg is vibrational in origin and the remainder configurational. At T&lt;Tg, the real component of Cp* varies more slowly with T than Cp,app.

Bibliography

Tombari, E., Ziparo, C., Salvetti, G., & Johari, G. P. (2007). Vibrational and configurational heat capacity of poly(vinyl acetate) from dynamic measurements. The Journal of Chemical Physics, 127(1).

Authors 4

E. Tombari (first)
C. Ziparo (additional)
G. Salvetti (additional)
G. P. Johari (additional)

References 32 Referenced 21

{'key': '2023080100060148900_c1', 'first-page': '185', 'volume': '25', 'year': '1956', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1956)
{'key': '2023080100060148900_c2', 'first-page': '372', 'volume': '28', 'year': '1958', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1958)
10.1063/1.1744275 / J. Chem. Phys. (1958)
10.1063/1.1696442 / J. Chem. Phys. (1965)
10.1063/1.325794 / J. Appl. Phys. (1979)
{'key': '2023080100060148900_c6', 'first-page': '387', 'volume': '307–310', 'year': '2002', 'journal-title': 'J. Non-Cryst. Solids'} / J. Non-Cryst. Solids (2002)
10.1103/PhysRevB.71.136201 / Phys. Rev. B (2005)
10.1063/1.2711206 / J. Chem. Phys. (2007)
10.1007/BF02189445 / Fortschr. Hochpolym.-Forsch. (1963)
10.1016/0040-6031(95)02552-9 / Thermochim. Acta (1995)
{'volume': '304–305', 'journal-title': 'Thermochim. Acta', 'year': '1997', 'key': '2023080100060148900_c10b'} / Thermochim. Acta (1997)
{'volume': '377', 'journal-title': 'Thermochim. Acta', 'year': '2001', 'key': '2023080100060148900_c10c'} / Thermochim. Acta (2001)
10.1016/S0040-6031(01)00493-2 / Thermochim. Acta (2001)
10.1016/S0040-6031(00)00645-6 / Thermochim. Acta (2000)
10.1021/jp025587d / J. Phys. Chem. B (2002)
10.1063/1.2432345 / J. Chem. Phys. (2007)
10.1063/1.2000228 / J. Chem. Phys. (2005)
10.1063/1.2711179 / J. Chem. Phys. (2007)
10.1002/jps.20601 / J. Pharm. Sci. (2006)
10.1016/0022-3093(94)90354-9 / J. Non-Cryst. Solids (1994)
10.1016/S0040-6031(01)00543-3 / Thermochim. Acta (2001)
10.1016/j.polymer.2005.10.097 / Polymer (2005)
10.1063/1.432063 / J. Chem. Phys. (1976)
{'key': '2023080100060148900_c22', 'first-page': '41', 'volume': '41', 'year': '1981', 'journal-title': 'Philos. Mag. B'} / Philos. Mag. B (1981)
10.1063/1.1679421 / J. Chem. Phys. (1973)
{'volume-title': 'Anelastic and Dielectric Effects in Polymeric Solids', 'year': '1967', 'key': '2023080100060148900_c24'} / Anelastic and Dielectric Effects in Polymeric Solids (1967)
10.1021/ma00016a036 / Macromolecules (1991)
10.1063/1.481349 / J. Chem. Phys. (2000)
10.1021/jp004420m / J. Phys. Chem. B (2001)
10.1111/j.1151-2916.1946.tb11592.x / J. Am. Ceram. Soc. (1946)
10.1063/1.479098 / J. Chem. Phys. (1999)
10.1016/S0022-3093(00)00432-4 / J. Non-Cryst. Solids (2001)

Dates

Type	When
Created	18 years, 1 month ago (July 7, 2007, 6:21 p.m.)
Deposited	2 years, 1 month ago (July 31, 2023, 8:06 p.m.)
Indexed	1 month ago (July 30, 2025, 6:48 a.m.)
Issued	18 years, 1 month ago (July 6, 2007)
Published	18 years, 1 month ago (July 6, 2007)
Published Online	18 years, 1 month ago (July 6, 2007)
Published Print	18 years, 1 month ago (July 7, 2007)

Funders 0

None

BibTeX

@article{Tombari_2007, title={Vibrational and configurational heat capacity of poly(vinyl acetate) from dynamic measurements}, volume={127}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.2747596}, DOI={10.1063/1.2747596}, number={1}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Tombari, E. and Ziparo, C. and Salvetti, G. and Johari, G. P.}, year={2007}, month=jul }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        7,
        30
      ]
    ],
    "date-time": "2025-07-30T10:48:35Z",
    "timestamp": 1753872515088,
    "version": "3.41.2"
  },
  "reference-count": 32,
  "publisher": "AIP Publishing",
  "issue": "1",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        2007,
        7,
        7
      ]
    ]
  },
  "abstract": "<jats:p>The complex heat capacity Cp* of poly(vinyl acetate) has been measured at 20.95mrad\u2215s modulation frequency during the cooling as well as on heating at 24, 8, and 2K\u2215h and during cooling at 0.5K\u2215h. The study is complemented with (the rate-dependent) Cp,app measured during cooling and heating at 60, 24, and 8K\u2215h. At low temperatures, the real component of Cp* yields the unrelaxed Cp or Cp,vib, the vibrational part of Cp. It is found to be indistinguishable from Cp,glass and lies on a line extrapolated to its equilibrium melt\u2019s temperature. At T near Tg,\u0394Cp(=Cp,melt\u2212Cp,glass) shows no detectable contribution from Cp,vib. The finding conflicts with a modified entropy theory calculation [E. A. DiMarzio and F. Dowell, J. Appl. Phys.\u200850, 6061 (1979)], which had predicted that \u223c27% of \u0394Cp of poly(vinyl acetate) at T near Tg is vibrational in origin and the remainder configurational. At T&amp;lt;Tg, the real component of Cp* varies more slowly with T than Cp,app.</jats:p>",
  "DOI": "10.1063/1.2747596",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2007,
        7,
        7
      ]
    ],
    "date-time": "2007-07-07T22:21:21Z",
    "timestamp": 1183846881000
  },
  "update-policy": "https://doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 21,
  "title": "Vibrational and configurational heat capacity of poly(vinyl acetate) from dynamic measurements",
  "prefix": "10.1063",
  "volume": "127",
  "author": [
    {
      "given": "E.",
      "family": "Tombari",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Istituto per i Processi Chimico-Fisici del CNR , via G. Moruzzi 1, 56124 Pisa, Italy"
        }
      ]
    },
    {
      "given": "C.",
      "family": "Ziparo",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Istituto per i Processi Chimico-Fisici del CNR , via G. Moruzzi 1, 56124 Pisa, Italy"
        }
      ]
    },
    {
      "given": "G.",
      "family": "Salvetti",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Istituto per i Processi Chimico-Fisici del CNR , via G. Moruzzi 1, 56124 Pisa, Italy"
        }
      ]
    },
    {
      "given": "G. P.",
      "family": "Johari",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "McMaster University Department of Materials Science and Engineering, , Hamilton, Ontario L8S 4L7, Canada"
        }
      ]
    }
  ],
  "member": "317",
  "published-online": {
    "date-parts": [
      [
        2007,
        7,
        6
      ]
    ]
  },
  "reference": [
    {
      "key": "2023080100060148900_c1",
      "first-page": "185",
      "volume": "25",
      "year": "1956",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c2",
      "first-page": "372",
      "volume": "28",
      "year": "1958",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c3",
      "doi-asserted-by": "publisher",
      "first-page": "807",
      "DOI": "10.1063/1.1744275",
      "volume": "28",
      "year": "1958",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c4",
      "doi-asserted-by": "publisher",
      "first-page": "139",
      "DOI": "10.1063/1.1696442",
      "volume": "43",
      "year": "1965",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c5",
      "doi-asserted-by": "publisher",
      "first-page": "6061",
      "DOI": "10.1063/1.325794",
      "volume": "50",
      "year": "1979",
      "journal-title": "J. Appl. Phys."
    },
    {
      "key": "2023080100060148900_c6",
      "first-page": "387",
      "volume": "307\u2013310",
      "year": "2002",
      "journal-title": "J. Non-Cryst. Solids"
    },
    {
      "key": "2023080100060148900_c7",
      "doi-asserted-by": "publisher",
      "first-page": "136201",
      "DOI": "10.1103/PhysRevB.71.136201",
      "volume": "71",
      "year": "2005",
      "journal-title": "Phys. Rev. B"
    },
    {
      "key": "2023080100060148900_c8",
      "doi-asserted-by": "publisher",
      "first-page": "114901",
      "DOI": "10.1063/1.2711206",
      "volume": "126",
      "year": "2007",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c9",
      "doi-asserted-by": "publisher",
      "first-page": "394",
      "DOI": "10.1007/BF02189445",
      "volume": "3",
      "year": "1963",
      "journal-title": "Fortschr. Hochpolym.-Forsch."
    },
    {
      "key": "2023080100060148900_c10a",
      "doi-asserted-by": "publisher",
      "first-page": "97",
      "DOI": "10.1016/0040-6031(95)02552-9",
      "volume": "266",
      "year": "1995",
      "journal-title": "Thermochim. Acta"
    },
    {
      "volume": "304\u2013305",
      "journal-title": "Thermochim. Acta",
      "year": "1997",
      "key": "2023080100060148900_c10b"
    },
    {
      "volume": "377",
      "journal-title": "Thermochim. Acta",
      "year": "2001",
      "key": "2023080100060148900_c10c"
    },
    {
      "key": "2023080100060148900_c11",
      "doi-asserted-by": "publisher",
      "first-page": "55",
      "DOI": "10.1016/S0040-6031(01)00493-2",
      "volume": "374",
      "year": "2001",
      "journal-title": "Thermochim. Acta"
    },
    {
      "key": "2023080100060148900_c12",
      "doi-asserted-by": "publisher",
      "first-page": "11",
      "DOI": "10.1016/S0040-6031(00)00645-6",
      "volume": "364",
      "year": "2000",
      "journal-title": "Thermochim. Acta"
    },
    {
      "key": "2023080100060148900_c13",
      "doi-asserted-by": "publisher",
      "first-page": "6081",
      "DOI": "10.1021/jp025587d",
      "volume": "106",
      "year": "2002",
      "journal-title": "J. Phys. Chem. B"
    },
    {
      "key": "2023080100060148900_c14",
      "doi-asserted-by": "publisher",
      "first-page": "021107",
      "DOI": "10.1063/1.2432345",
      "volume": "126",
      "year": "2007",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c15",
      "doi-asserted-by": "publisher",
      "first-page": "051104",
      "DOI": "10.1063/1.2000228",
      "volume": "123",
      "year": "2005",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c16",
      "doi-asserted-by": "publisher",
      "first-page": "124506",
      "DOI": "10.1063/1.2711179",
      "volume": "126",
      "year": "2007",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c17",
      "doi-asserted-by": "publisher",
      "first-page": "1006",
      "DOI": "10.1002/jps.20601",
      "volume": "95",
      "year": "2006",
      "journal-title": "J. Pharm. Sci."
    },
    {
      "key": "2023080100060148900_c18",
      "doi-asserted-by": "publisher",
      "first-page": "182",
      "DOI": "10.1016/0022-3093(94)90354-9",
      "volume": "171",
      "year": "1994",
      "journal-title": "J. Non-Cryst. Solids"
    },
    {
      "key": "2023080100060148900_c19",
      "doi-asserted-by": "publisher",
      "first-page": "85",
      "DOI": "10.1016/S0040-6031(01)00543-3",
      "volume": "377",
      "year": "2001",
      "journal-title": "Thermochim. Acta"
    },
    {
      "key": "2023080100060148900_c20",
      "doi-asserted-by": "publisher",
      "first-page": "12240",
      "DOI": "10.1016/j.polymer.2005.10.097",
      "volume": "46",
      "year": "2005",
      "journal-title": "Polymer"
    },
    {
      "key": "2023080100060148900_c21",
      "doi-asserted-by": "publisher",
      "first-page": "4767",
      "DOI": "10.1063/1.432063",
      "volume": "64",
      "year": "1976",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c22",
      "first-page": "41",
      "volume": "41",
      "year": "1981",
      "journal-title": "Philos. Mag. B"
    },
    {
      "key": "2023080100060148900_c23",
      "doi-asserted-by": "publisher",
      "first-page": "1766",
      "DOI": "10.1063/1.1679421",
      "volume": "58",
      "year": "1973",
      "journal-title": "J. Chem. Phys."
    },
    {
      "volume-title": "Anelastic and Dielectric Effects in Polymeric Solids",
      "year": "1967",
      "key": "2023080100060148900_c24"
    },
    {
      "key": "2023080100060148900_c25",
      "doi-asserted-by": "publisher",
      "first-page": "4713",
      "DOI": "10.1021/ma00016a036",
      "volume": "24",
      "year": "1991",
      "journal-title": "Macromolecules"
    },
    {
      "key": "2023080100060148900_c26",
      "doi-asserted-by": "publisher",
      "first-page": "7518",
      "DOI": "10.1063/1.481349",
      "volume": "112",
      "year": "2000",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c27",
      "doi-asserted-by": "publisher",
      "first-page": "3600",
      "DOI": "10.1021/jp004420m",
      "volume": "105",
      "year": "2001",
      "journal-title": "J. Phys. Chem. B"
    },
    {
      "key": "2023080100060148900_c28",
      "doi-asserted-by": "publisher",
      "first-page": "240",
      "DOI": "10.1111/j.1151-2916.1946.tb11592.x",
      "volume": "29",
      "year": "1946",
      "journal-title": "J. Am. Ceram. Soc."
    },
    {
      "key": "2023080100060148900_c29",
      "doi-asserted-by": "publisher",
      "first-page": "11592",
      "DOI": "10.1063/1.479098",
      "volume": "110",
      "year": "1999",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2023080100060148900_c30",
      "doi-asserted-by": "publisher",
      "first-page": "91",
      "DOI": "10.1016/S0022-3093(00)00432-4",
      "volume": "281",
      "year": "2001",
      "journal-title": "J. Non-Cryst. Solids"
    }
  ],
  "container-title": "The Journal of Chemical Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.2747596/15400206/014905_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.2747596/15400206/014905_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2023,
        8,
        1
      ]
    ],
    "date-time": "2023-08-01T00:06:13Z",
    "timestamp": 1690848373000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/127/1/014905/906480/Vibrational-and-configurational-heat-capacity-of"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        2007,
        7,
        6
      ]
    ]
  },
  "references-count": 32,
  "journal-issue": {
    "issue": "1",
    "published-print": {
      "date-parts": [
        [
          2007,
          7,
          7
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.2747596",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        2007,
        7,
        7
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        2007,
        7,
        6
      ]
    ]
  },
  "article-number": "014905"
}