(Way 20, ‘The enthalpies of cmmbuntn and fa ine eae combuation and forma i Key words reference polymer Introduction Linear polyethylene, although well-known as material for containers, is also used as a standard reference material in polymer research and technology. However, it is not definite chemical compound, ing in the proportion of meth density and degree of cryst ‘ Standard Reference Materials (OSRM) has made available a sample of linear polyethylene, the ties of which have been carefully studied. This in- ‘vestigation was undertaken to determine the effect of the degree of crystallinity on the enthalpies of com: bustion and formation. In order to make 4 study of this type it was necessary to obtain at Jeast two samples aay nearly identical as ponsible excent for the degen tallinity, We were fortunate to obtain such ate tone of which had been formed by recrystalli- Zation of the other under high pressure. Since the Hoot on the enthalpy of combustion was expected to be small, a high-precision measurement was required. 2. Materials 2.1. Polyethylene in these experiments is NBS Yer oe ara (SRM) 1475. According The polyeth standard Refere jes of Combustion and F of Linear Polyethylene 1974) ‘ot two samples of linear polyethslone which differ ‘have been determined in an oxygen bomb calorimeter, ‘the enthalpy f combustion at 29815 Kan the enthalpy of fora: fine aia oR mang a role o li Unensines tid scene area ‘thalpy: heat of combustion; heat of erystalization: heat of formation; polymer; standard to the certificate issued by the OSRM it is a ct EI duPoor ds Nemours aad. Couigaaie fessentialy linear, there being. 015. methyl. per 100 carbon atoms This inthe fori of small 2'to 3 mm in diameter; the degree of ery deter be 2 percent Recording wo the ante facturer, 111 ppm of an antioxidant (CsHoiOu atlded ta the polyethylene. ees ‘A modification of SRM 1475 resulting from Yeerys talliation of the melt under high. pressure. was ob- ined in the form of chips through the courtesy of S.'S. Chang (1[t of the Institute for Materials Re- search at the NBS. The degree of crystallinity forthe modified material was determined to be 96 percent ‘The degrees of eryetaliity of the two samples were determined by Dr. Chang from density measurements. 2.2, Benzoie Acid The benzoic acid was SRM 39, which is used as a standard for oxygen-bomb calorimetry. The energy of combustion under certificate conditions was certified to be 26434 J/g. Conversion to thermodynamic stand: frd state conditions using the same data reduction procedure described in section 5 gave AUC(@B °C) = 260610.36 Je.