DOI: 10.1002/pol.1968.160060115. Kinetic interpretation of the glass transition: Glass temperatures of <i>n</i>‐alkane liquids and polyethylene

Kinetic interpretation of the glass transition: Glass temperatures of n‐alkane liquids and polyethylene

10.1002/pol.1968.160060115

Crossref journal-article

Wiley

Journal of Polymer Science Part A-2: Polymer Physics (311)

Abstract

AbstractOn the basis of an isoviscosity criterion for the glass transition (ηg ⋍ 1013 poise) in liquids of low molecular weight, theoretical Tg values were calculated for the n‐alkane series by the equation log η = log A + B/(T − T0), with the use of values reported by Lewis for the parameters. The Tg/T0 ratio reaches a limiting value of 1.25 and ϕg = (Tg − T0)/2.3B = 0.027, a constant. Extrapolation to (CH2)∞ gives Tg = 200°K., T0 = 160°K., and B = 640°K. This Tg is consistent with other estimates for poly‐ethylene, and T0 coincides with the temperature at which the “excess” liquid entropy for (CH2)∞ becomes zero from thermodynamic data. For polymer liquids it is proposed that E0 = 2.3RB is determined by the internal barriers to rotation for the “isolated” polymer chains. Thus, E0 = 2.9 kcal./mole for polyethylene, 3.0 kcal./mole for polystyrene, 5.7 kcal./mole for polyisobutylene, and 1.9 kcal./mole for polydimethylsiloxane.

Bibliography

Miller, A. A. (1968). Kinetic interpretation of the glass transition: Glass temperatures of nâalkane liquids and polyethylene. Journal of Polymer Science Part A-2: Polymer Physics, 6(1), 249â257. Portico.

Authors 1

A. A. Miller (first)

References 28 Referenced 32

{'key': 'e_1_2_1_2_2', 'first-page': '645', 'volume': '22', 'author': 'Vogel H.', 'year': '1921', 'journal-title': 'Physik. Z.'} / Physik. Z. by Vogel H. (1921)
10.1111/j.1151-2916.1925.tb16731.x
10.1002/zaac.19261560121
10.1063/1.1699711
10.1002/pol.1964.100020307
10.1063/1.1744141
10.1063/1.1697197
10.1063/1.1700096
10.5254/1.3539649
10.1002/pol.1960.1204614810
10.1002/jctb.5010140201
Selected Properties of Hydrocarbons A. P. I. Project 44 Carnegie Press 1953 Table 20d (Part 1).
10.1063/1.1699894
10.1021/j100893a514
10.1016/0032-3861(63)90028-4
10.1021/j150521a001
10.1002/pol.1966.160040311
10.1002/pol.1956.1202210211
10.6028/jres.067A.023
10.1063/1.1696442
10.1063/1.1729095
10.1021/j100892a030
10.1002/app.1963.070070111
{'key': 'e_1_2_1_25_2', 'first-page': '70', 'volume-title': 'Configurational Statistics of Polymer Chains', 'author': 'Volkenstein M. V.', 'year': '1963'} / Configurational Statistics of Polymer Chains by Volkenstein M. V. (1963)
10.1002/jctb.5010140101
10.1098/rspa.1964.0229
10.1063/1.1725872
10.1063/1.1725086

Dates

Type	When
Created	22 years, 4 months ago (April 21, 2003, 2:46 a.m.)
Deposited	1 year, 9 months ago (Nov. 1, 2023, 12:49 p.m.)
Indexed	1 year, 6 months ago (Feb. 11, 2024, 1:21 a.m.)
Issued	57 years, 7 months ago (Jan. 1, 1968)
Published	57 years, 7 months ago (Jan. 1, 1968)
Published Online	22 years, 5 months ago (March 10, 2003)
Published Print	57 years, 7 months ago (Jan. 1, 1968)

Funders 0

None

BibTeX

@article{Miller_1968, title={Kinetic interpretation of the glass transition: Glass temperatures of n‐alkane liquids and polyethylene}, volume={6}, ISSN={1542-9377}, url={http://dx.doi.org/10.1002/pol.1968.160060115}, DOI={10.1002/pol.1968.160060115}, number={1}, journal={Journal of Polymer Science Part A-2: Polymer Physics}, publisher={Wiley}, author={Miller, A. A.}, year={1968}, month=jan, pages={249–257} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2024,
        2,
        11
      ]
    ],
    "date-time": "2024-02-11T06:21:55Z",
    "timestamp": 1707632515957
  },
  "reference-count": 28,
  "publisher": "Wiley",
  "issue": "1",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            2003,
            3,
            10
          ]
        ],
        "date-time": "2003-03-10T00:00:00Z",
        "timestamp": 1047254400000
      },
      "content-version": "vor",
      "delay-in-days": 12852,
      "URL": "http://onlinelibrary.wiley.com/termsAndConditions#vor"
    }
  ],
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        1968,
        1
      ]
    ]
  },
  "abstract": "<jats:title>Abstract</jats:title><jats:p>On the basis of an isoviscosity criterion for the glass transition (\u03b7<jats:sub><jats:italic>g</jats:italic></jats:sub> \u22cd 10<jats:sup>13</jats:sup> poise) in liquids of low molecular weight, theoretical <jats:italic>T</jats:italic><jats:sub><jats:italic>g</jats:italic></jats:sub> values were calculated for the <jats:italic>n</jats:italic>\u2010alkane series by the equation log \u03b7 = log <jats:italic>A</jats:italic> + <jats:italic>B</jats:italic>/(<jats:italic>T</jats:italic> \u2212 <jats:italic>T</jats:italic><jats:sub>0</jats:sub>), with the use of values reported by Lewis for the parameters. The <jats:italic>T</jats:italic><jats:sub><jats:italic>g</jats:italic></jats:sub>/<jats:italic>T</jats:italic><jats:sub>0</jats:sub> ratio reaches a limiting value of 1.25 and \u03d5<jats:sub><jats:italic>g</jats:italic></jats:sub> = (<jats:italic>T</jats:italic><jats:sub><jats:italic>g</jats:italic></jats:sub> \u2212 <jats:italic>T</jats:italic><jats:sub>0</jats:sub>)/2.3<jats:italic>B</jats:italic> = 0.027, a constant. Extrapolation to (CH<jats:sub>2</jats:sub>)<jats:sub>\u221e</jats:sub> gives <jats:italic>T</jats:italic><jats:sub><jats:italic>g</jats:italic></jats:sub> = 200\u00b0K., <jats:italic>T</jats:italic><jats:sub>0</jats:sub> = 160\u00b0K., and <jats:italic>B</jats:italic> = 640\u00b0K. This <jats:italic>T</jats:italic><jats:sub><jats:italic>g</jats:italic></jats:sub> is consistent with other estimates for poly\u2010ethylene, and <jats:italic>T</jats:italic><jats:sub>0</jats:sub> coincides with the temperature at which the \u201cexcess\u201d liquid entropy for (CH<jats:sub>2</jats:sub>)<jats:sub>\u221e</jats:sub> becomes zero from thermodynamic data. For polymer liquids it is proposed that <jats:italic>E</jats:italic><jats:sub>0</jats:sub> = 2.3<jats:italic>RB</jats:italic> is determined by the internal barriers to rotation for the \u201cisolated\u201d polymer chains. Thus, <jats:italic>E</jats:italic><jats:sub>0</jats:sub> = 2.9 kcal./mole for polyethylene, 3.0 kcal./mole for polystyrene, 5.7 kcal./mole for polyisobutylene, and 1.9 kcal./mole for polydimethylsiloxane.</jats:p>",
  "DOI": "10.1002/pol.1968.160060115",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2003,
        4,
        21
      ]
    ],
    "date-time": "2003-04-21T06:46:28Z",
    "timestamp": 1050907588000
  },
  "page": "249-257",
  "source": "Crossref",
  "is-referenced-by-count": 32,
  "title": "Kinetic interpretation of the glass transition: Glass temperatures of <i>n</i>\u2010alkane liquids and polyethylene",
  "prefix": "10.1002",
  "volume": "6",
  "author": [
    {
      "given": "A. A.",
      "family": "Miller",
      "sequence": "first",
      "affiliation": []
    }
  ],
  "member": "311",
  "published-online": {
    "date-parts": [
      [
        2003,
        3,
        10
      ]
    ]
  },
  "reference": [
    {
      "key": "e_1_2_1_2_2",
      "first-page": "645",
      "volume": "22",
      "author": "Vogel H.",
      "year": "1921",
      "journal-title": "Physik. Z."
    },
    {
      "key": "e_1_2_1_3_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1111/j.1151-2916.1925.tb16731.x"
    },
    {
      "key": "e_1_2_1_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/zaac.19261560121"
    },
    {
      "key": "e_1_2_1_5_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1699711"
    },
    {
      "key": "e_1_2_1_6_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1964.100020307"
    },
    {
      "key": "e_1_2_1_7_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1744141"
    },
    {
      "key": "e_1_2_1_8_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1697197"
    },
    {
      "key": "e_1_2_1_9_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1700096"
    },
    {
      "key": "e_1_2_1_10_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.5254/1.3539649"
    },
    {
      "key": "e_1_2_1_11_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1960.1204614810"
    },
    {
      "key": "e_1_2_1_12_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/jctb.5010140201"
    },
    {
      "key": "e_1_2_1_13_2",
      "unstructured": "Selected Properties of Hydrocarbons A. P. I. Project 44 Carnegie Press 1953 Table 20d (Part 1)."
    },
    {
      "key": "e_1_2_1_14_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1699894"
    },
    {
      "key": "e_1_2_1_15_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/j100893a514"
    },
    {
      "key": "e_1_2_1_16_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0032-3861(63)90028-4"
    },
    {
      "key": "e_1_2_1_17_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/j150521a001"
    },
    {
      "key": "e_1_2_1_18_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1966.160040311"
    },
    {
      "key": "e_1_2_1_19_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1956.1202210211"
    },
    {
      "key": "e_1_2_1_20_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.6028/jres.067A.023"
    },
    {
      "key": "e_1_2_1_21_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1696442"
    },
    {
      "key": "e_1_2_1_22_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1729095"
    },
    {
      "key": "e_1_2_1_23_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/j100892a030"
    },
    {
      "key": "e_1_2_1_24_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/app.1963.070070111"
    },
    {
      "key": "e_1_2_1_25_2",
      "first-page": "70",
      "volume-title": "Configurational Statistics of Polymer Chains",
      "author": "Volkenstein M. V.",
      "year": "1963"
    },
    {
      "key": "e_1_2_1_26_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/jctb.5010140101"
    },
    {
      "key": "e_1_2_1_27_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1098/rspa.1964.0229"
    },
    {
      "key": "e_1_2_1_28_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1725872"
    },
    {
      "key": "e_1_2_1_29_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1725086"
    }
  ],
  "container-title": "Journal of Polymer Science Part A-2: Polymer Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fpol.1968.160060115",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/pdf/10.1002/pol.1968.160060115",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2023,
        11,
        1
      ]
    ],
    "date-time": "2023-11-01T16:49:41Z",
    "timestamp": 1698857381000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://onlinelibrary.wiley.com/doi/10.1002/pol.1968.160060115"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1968,
        1
      ]
    ]
  },
  "references-count": 28,
  "journal-issue": {
    "issue": "1",
    "published-print": {
      "date-parts": [
        [
          1968,
          1
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1002/pol.1968.160060115"
  ],
  "URL": "http://dx.doi.org/10.1002/pol.1968.160060115",
  "relation": {},
  "ISSN": [
    "0449-2978",
    "1542-9377"
  ],
  "subject": [],
  "container-title-short": "J. Polym. Sci. A\u20102 Polym. Phys.",
  "published": {
    "date-parts": [
      [
        1968,
        1
      ]
    ]
  }
}