DOI: 10.1002/macp.1968.021180104. Phase changes in polyethylene single crystals. The effects of thermal stress and electron irradiation

Phase changes in polyethylene single crystals. The effects of thermal stress and electron irradiation

10.1002/macp.1968.021180104

Crossref journal-article

Wiley

Die Makromolekulare Chemie (311)

Abstract

AbstractSingle crystals of polyethylene have been reported to undergo a crystallographic phase change from an orthorhombic unit cell to monoclinic when heated to temperatures near their original crystallization temperatures. This change is shown to be due purely to thermal stresses set up between the crystals and substrate on which they lie, arising from a difference in expansion coefficients of crystals and substrate. The orientation of the monoclinic lattice with respect to the orthorhombic lattice is consistent with an effective deformation parallel to the orthorhombic b‐axis. At temperatures above 110°C the monoclinic phase relaxes almost completely back to orthorhombic primarily through the greatly increased mobility of the chains in their folded portions. The effects of an electron beam on the polyethylene crystal lattice have been studied by electron diffraction during irradiation at temperatures from −161 to + 110°C. The changes in dimensions of the unit (sub)‐cell were determined as functions of the time of irradiation. Above about 30°C a stable hexagonal phase is formed before the crystalline diffraction pattern degrades to a diffuse halo. This change is ascribed to (i) a depression of a transition temperature (due to defects) analogous to that found in n‐paraffins when the orthorhombic unit cell becomes hexagonal, and (ii) elastic distortions around the lattice defects. It is also noted that the transformation proceeds readily at 110°C in the absence of radiation if a small dose is given initially: the number of defects under these conditions are few and consequently on cooling to room temperature the hexagonal and orthorhombic phase co‐exist. Although no definitive conclusions as to the nature of the reaction can be determined, the evidence is that the defects are primarily scissions and cross‐links in the crystal lattice.

Bibliography

Kiho, H., & Ingram, P. (1968). Phase changes in polyethylene single crystals. The effects of thermal stress and electron irradiation. Die Makromolekulare Chemie, 118(1), 45â59. Portico.

Authors 2

H. Kiho (first)
P. Ingram (additional)

References 37 Referenced 24

{'key': 'e_1_2_1_1_2', 'first-page': '292', 'volume': '6', 'author': 'Tanaka K.', 'year': '1963', 'journal-title': 'Rep. Progr. Polymer Physics Japan'} / Rep. Progr. Polymer Physics Japan by Tanaka K. (1963)
10.1002/pol.1964.100020902
10.1063/1.1713673
10.1063/1.1713204
10.1002/macp.1965.020880113
K.Sakaoku Ph.D. Thesis Kyoto University Japan1964.
{'key': 'e_1_2_1_7_2', 'first-page': '359', 'volume': '14', 'author': 'Kobayashi K.', 'year': '1965', 'journal-title': 'Lab. Invest.'} / Lab. Invest. by Kobayashi K. (1965)
10.1002/j.1538-7305.1960.tb01619.x
10.1515/zna-1949-0107 / Z. Naturforsch. by Von Borries B. (1949)
10.1515/zna-1954-0301 / Z. Naturforsch. by Lenz F. (1954)
{'key': 'e_1_2_1_10_2', 'volume-title': 'Tabellen der Elektrouphysik', 'author': 'Ardenne M. V.', 'year': '1956'} / Tabellen der Elektrouphysik by Ardenne M. V. (1956)
10.1103/RevModPhys.28.184
10.1080/14786436308207335
10.1002/pol.1965.110030404
10.1002/pol.1960.1204614722
10.1002/pol.1965.110030217
10.1016/0032-3861(66)90073-5
10.1016/0032-3861(63)90032-6
{'key': 'e_1_2_1_18_2', 'first-page': '445', 'volume-title': 'Polymer Single Crystals', 'author': 'Geil P. H.', 'year': '1963'} / Polymer Single Crystals by Geil P. H. (1963)
10.1002/pol.1965.110030405
10.1007/BF01520390
10.1002/app.1960.070030913
{'key': 'e_1_2_1_22_2', 'first-page': '77', 'volume': '42', 'author': 'Sakurada I.', 'year': '1964', 'journal-title': 'Bull. Inst. chem. Res., Kyoto Univ.'} / Bull. Inst. chem. Res., Kyoto Univ. by Sakurada I. (1964)
{'key': 'e_1_2_1_23_2', 'volume-title': 'Radiation Chemistry of Polymeric Systems', 'author': 'Chapiro A.', 'year': '1962'} / Radiation Chemistry of Polymeric Systems by Chapiro A. (1962)
10.1021/j150539a021
10.1063/1.1731155
10.1021/j150561a022
10.1002/pol.1964.110020508
10.1002/pol.1964.110021104
10.1016/0032-3861(60)90044-6
10.1016/0032-3861(60)90045-8
10.1002/j.1538-7305.1961.tb03257.x
10.1063/1.1713201
10.1002/pol.1964.110020817
10.1080/14786436408225383
10.1080/14786436508218906
10.1002/pol.1965.110030609

Dates

Type	When
Created	22 years, 4 months ago (April 15, 2003, 6:58 p.m.)
Deposited	1 year, 9 months ago (Nov. 13, 2023, 7:05 p.m.)
Indexed	1 year, 6 months ago (Feb. 7, 2024, 6:44 p.m.)
Issued	56 years, 9 months ago (Nov. 19, 1968)
Published	56 years, 9 months ago (Nov. 19, 1968)
Published Online	22 years, 5 months ago (March 12, 2003)
Published Print	56 years, 9 months ago (Nov. 19, 1968)

Funders 0

None

BibTeX

@article{Kiho_1968, title={Phase changes in polyethylene single crystals. The effects of thermal stress and electron irradiation}, volume={118}, ISSN={0025-116X}, url={http://dx.doi.org/10.1002/macp.1968.021180104}, DOI={10.1002/macp.1968.021180104}, number={1}, journal={Die Makromolekulare Chemie}, publisher={Wiley}, author={Kiho, H. and Ingram, P.}, year={1968}, month=nov, pages={45–59} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2024,
        2,
        7
      ]
    ],
    "date-time": "2024-02-07T23:44:38Z",
    "timestamp": 1707349478588
  },
  "reference-count": 37,
  "publisher": "Wiley",
  "issue": "1",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            2003,
            3,
            12
          ]
        ],
        "date-time": "2003-03-12T00:00:00Z",
        "timestamp": 1047427200000
      },
      "content-version": "vor",
      "delay-in-days": 12531,
      "URL": "http://onlinelibrary.wiley.com/termsAndConditions#vor"
    }
  ],
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        1968,
        11,
        19
      ]
    ]
  },
  "abstract": "<jats:title>Abstract</jats:title><jats:p>Single crystals of polyethylene have been reported to undergo a crystallographic phase change from an orthorhombic unit cell to monoclinic when heated to temperatures near their original crystallization temperatures. This change is shown to be due purely to thermal stresses set up between the crystals and substrate on which they lie, arising from a difference in expansion coefficients of crystals and substrate. The orientation of the monoclinic lattice with respect to the orthorhombic lattice is consistent with an effective deformation parallel to the orthorhombic <jats:italic>b</jats:italic>\u2010axis. At temperatures above 110\u00b0C the monoclinic phase relaxes almost completely back to orthorhombic primarily through the greatly increased mobility of the chains in their folded portions. The effects of an electron beam on the polyethylene crystal lattice have been studied by electron diffraction during irradiation at temperatures from \u2212161 to + 110\u00b0C. The changes in dimensions of the unit (sub)\u2010cell were determined as functions of the time of irradiation. Above about 30\u00b0C a stable hexagonal phase is formed before the crystalline diffraction pattern degrades to a diffuse halo. This change is ascribed to (i) a depression of a transition temperature (due to defects) analogous to that found in <jats:italic>n</jats:italic>\u2010paraffins when the orthorhombic unit cell becomes hexagonal, and (ii) elastic distortions around the lattice defects. It is also noted that the transformation proceeds readily at 110\u00b0C in the absence of radiation if a small dose is given initially: the number of defects under these conditions are few and consequently on cooling to room temperature the hexagonal and orthorhombic phase co\u2010exist. Although no definitive conclusions as to the nature of the reaction can be determined, the evidence is that the defects are primarily scissions and cross\u2010links in the crystal lattice.</jats:p>",
  "DOI": "10.1002/macp.1968.021180104",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2003,
        4,
        15
      ]
    ],
    "date-time": "2003-04-15T22:58:21Z",
    "timestamp": 1050447501000
  },
  "page": "45-59",
  "source": "Crossref",
  "is-referenced-by-count": 24,
  "title": "Phase changes in polyethylene single crystals. The effects of thermal stress and electron irradiation",
  "prefix": "10.1002",
  "volume": "118",
  "author": [
    {
      "given": "H.",
      "family": "Kiho",
      "sequence": "first",
      "affiliation": []
    },
    {
      "given": "P.",
      "family": "Ingram",
      "sequence": "additional",
      "affiliation": []
    }
  ],
  "member": "311",
  "published-online": {
    "date-parts": [
      [
        2003,
        3,
        12
      ]
    ]
  },
  "reference": [
    {
      "key": "e_1_2_1_1_2",
      "first-page": "292",
      "volume": "6",
      "author": "Tanaka K.",
      "year": "1963",
      "journal-title": "Rep. Progr. Polymer Physics Japan"
    },
    {
      "key": "e_1_2_1_2_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1964.100020902"
    },
    {
      "key": "e_1_2_1_3_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1713673"
    },
    {
      "key": "e_1_2_1_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1713204"
    },
    {
      "key": "e_1_2_1_5_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/macp.1965.020880113"
    },
    {
      "key": "e_1_2_1_6_2",
      "unstructured": "K.Sakaoku Ph.D. Thesis Kyoto University Japan1964."
    },
    {
      "key": "e_1_2_1_7_2",
      "first-page": "359",
      "volume": "14",
      "author": "Kobayashi K.",
      "year": "1965",
      "journal-title": "Lab. Invest."
    },
    {
      "key": "e_1_2_1_8_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/j.1538-7305.1960.tb01619.x"
    },
    {
      "key": "e_1_2_1_9_2",
      "doi-asserted-by": "crossref",
      "first-page": "51",
      "DOI": "10.1515/zna-1949-0107",
      "volume": "4",
      "author": "Von Borries B.",
      "year": "1949",
      "journal-title": "Z. Naturforsch."
    },
    {
      "key": "e_1_2_1_9_3",
      "doi-asserted-by": "crossref",
      "first-page": "185",
      "DOI": "10.1515/zna-1954-0301",
      "volume": "9",
      "author": "Lenz F.",
      "year": "1954",
      "journal-title": "Z. Naturforsch."
    },
    {
      "key": "e_1_2_1_10_2",
      "volume-title": "Tabellen der Elektrouphysik",
      "author": "Ardenne M. V.",
      "year": "1956"
    },
    {
      "key": "e_1_2_1_11_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1103/RevModPhys.28.184"
    },
    {
      "key": "e_1_2_1_12_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1080/14786436308207335"
    },
    {
      "key": "e_1_2_1_13_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1965.110030404"
    },
    {
      "key": "e_1_2_1_14_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1960.1204614722"
    },
    {
      "key": "e_1_2_1_15_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1965.110030217"
    },
    {
      "key": "e_1_2_1_16_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0032-3861(66)90073-5"
    },
    {
      "key": "e_1_2_1_17_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0032-3861(63)90032-6"
    },
    {
      "key": "e_1_2_1_18_2",
      "first-page": "445",
      "volume-title": "Polymer Single Crystals",
      "author": "Geil P. H.",
      "year": "1963"
    },
    {
      "key": "e_1_2_1_19_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1965.110030405"
    },
    {
      "key": "e_1_2_1_20_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1007/BF01520390"
    },
    {
      "key": "e_1_2_1_21_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/app.1960.070030913"
    },
    {
      "key": "e_1_2_1_22_2",
      "first-page": "77",
      "volume": "42",
      "author": "Sakurada I.",
      "year": "1964",
      "journal-title": "Bull. Inst. chem. Res., Kyoto Univ."
    },
    {
      "key": "e_1_2_1_23_2",
      "volume-title": "Radiation Chemistry of Polymeric Systems",
      "author": "Chapiro A.",
      "year": "1962"
    },
    {
      "key": "e_1_2_1_24_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/j150539a021"
    },
    {
      "key": "e_1_2_1_25_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1731155"
    },
    {
      "key": "e_1_2_1_26_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/j150561a022"
    },
    {
      "key": "e_1_2_1_27_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1964.110020508"
    },
    {
      "key": "e_1_2_1_27_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1964.110021104"
    },
    {
      "key": "e_1_2_1_28_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0032-3861(60)90044-6"
    },
    {
      "key": "e_1_2_1_29_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0032-3861(60)90045-8"
    },
    {
      "key": "e_1_2_1_30_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/j.1538-7305.1961.tb03257.x"
    },
    {
      "key": "e_1_2_1_31_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.1713201"
    },
    {
      "key": "e_1_2_1_31_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1964.110020817"
    },
    {
      "key": "e_1_2_1_32_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1080/14786436408225383"
    },
    {
      "key": "e_1_2_1_32_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1080/14786436508218906"
    },
    {
      "key": "e_1_2_1_33_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1965.110030609"
    }
  ],
  "container-title": "Die Makromolekulare Chemie",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fmacp.1968.021180104",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.1968.021180104",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2023,
        11,
        14
      ]
    ],
    "date-time": "2023-11-14T00:05:12Z",
    "timestamp": 1699920312000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://onlinelibrary.wiley.com/doi/10.1002/macp.1968.021180104"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1968,
        11,
        19
      ]
    ]
  },
  "references-count": 37,
  "journal-issue": {
    "issue": "1",
    "published-print": {
      "date-parts": [
        [
          1968,
          11,
          19
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1002/macp.1968.021180104"
  ],
  "URL": "http://dx.doi.org/10.1002/macp.1968.021180104",
  "relation": {},
  "ISSN": [
    "0025-116X",
    "0025-116X"
  ],
  "subject": [],
  "container-title-short": "Makromol. Chem.",
  "published": {
    "date-parts": [
      [
        1968,
        11,
        19
      ]
    ]
  }
}