PP. Phys, Vol. 12 1979. Printed in Great Britain Ne investigation in Fischer-Tropsch waxes JAJ Lourens and EC Reynhardt Department of Physics, University of South Africa, PO Box 3 Pretoria, South Afiiea Received 8 May 1979 Abstract. An investigation of the proton second moment and nuclear spn-atice n time a8 a function of temperature in two Fischer-Tropsch waxes having age carbon numbers of 28 and 285s reported. The temperature dependence ofthe motional behaviour of the chains inthe wanes differs significantly from the behaviour in the normal compound mCssHoa. As revealed by the second moment measurements, the rotational-iisional (no ainsi the waves st in ot te tures much below the transition to the hexagonal phase, The results are consistent with ‘4 model in which the chains of unequal length in the erysalline zones of the waxes are packed in an irregular, staggered arrangement. ‘The onset of the RoD motions in the is preceded by structural phase transitions which occur a temperatures depending fin the range of rs in each wax. Activation energies forthe diferent molecular motions are reported and compared with corresponding values in n-CesFsa mations of th 1, Tntroduetion ‘The products of the Fischer-Tropsch synthesis are mainly mixtures of normal and branched paraffins and olefins. Fischer-Tropsch waxes are produced on a large scale by the *Arge’ version of the synthesis which wa Germany. Apart from the obvious uses of waxes in producing eandles and polish, they form important raw materials in the manufacturing of produets such as ceramics, food, rubber, timber, textiles, tobacco, paint, plastics, etc. The collection and interpretation of fundamental data on waxes are therefore, a primary objective of industries which employ the ‘Arge’ version of the Fischer-Tropsch synthesis and consequently a great deal of research has been carried out on Fischer-Tropsch waxes. The investigation of structural aspects such as crystallinity and branching of the chain-like molecules by means of spectrometric and diffraction methods has led to a proposal of a structural ‘model of a paraffinic Fischer-Tropsch wax consisting of crystalline, rigid amorphous and mobile amorphous phases. The dependence of hardness, congealing point and density ‘on molecular mass and crystallinity has been reported (Le Roux 1969a,b,¢, 1970, Le Roux et al 1976). These properties increase with increasing molecular mass although the crystallinities of the waxes were found to be independent of their densities. In addition, ‘measurements of the thermal expansion and thermal conductivity of the waxes have been carried out as a function of temperature, mostly from room temperature upwards (Le Roux et al 1974). While proton magnetic resonance studies (Andrew 1949, Odajima et al 1962, Olf and Peterlin 1970a,b,c, Anderson and Slichter 1965, Ewen er al 1974) of the normal long- chain paraffins, 1-CyuHens2 (1-Cy), have yielded valuable information regarding mol- on 727/79/111963 +11 $01.00 © 1979 The Institute of Physics1964 J Ad Lourens and EC Reynhardt cular reorientations and phase transitions, similar investigations have not been reported for Fischer-Tropsch waxes, Since the physical properties of Cys are to a large extent determined by chain length and chain motion, it is of considerable interest to investigate the motional behiaviour of chains in a paraffinic wax containing a range of 7-paraffins. In this paper we report the results of a detailed investigation of the variation of the second moment (Ms) and the nuclear spin-lattice relaxation time (7i) with temperature of two Fischer-Tropsch waxes, Ceasy and C.es.s9, having chain-length disorder values Ar of 4:12 and 1-81 carbon numbers respectively. These numbers are simply the root mean square deviations from the average carbon numbers, 28 and 28-5. It has been found that the temperature dependence of the motional behaviour of the chains in these waxes differs significantly from the behaviour in the normal compound 1-Ces, The various molecular reorientations have been identified and compared with similar motions in ‘n-Cag. ‘The structural phase transitions are discussed, activation energies for the different molecular motions reported and discrepancies between the results for the waxes and Cy of comparable chain lengths are explained in terms of structural differences, The results are consistent with a model in which the chains of unequal length in the erystalline zones of the waxes are packed in an irregular, staggered arrangement. 2, Struetnre Pure Cy crystals are known to exist in four erystal modifications (McClure 1968). Paraffins with even carbon numbers from 18 to 24 are trielinic, n-Cog can be either mono- clinic or triclinic while those from 28 to 38 are monoclinic. For odd m, all the paraffins are orthorliombie at room temperature. The fourth modification is that of the hexagonal or quasi-hexagonal state which results from the first-order phase transition a few degrees below the melting point. On the other hand waxes, containing impurities, cannot exist in any of the modifications mentioned above. They are orthorhombic with a different space group (Smith 1953, Miller 1928, 1932) irrespective of whether the main compo- nents have even or odd carbon numbers. According to the thermal expansion measur ments of Templin (1963), the phase transition and melting points of n-Cy tend to converge above and below 1-Cs2 as m increases or decreases from 32. For example both 1-Cyo and Cio do not have solid-solid transition points distinct from the melting point, while solid-solid transition occurs in m-Czs, about 6 K below the melting point of 332K ‘n-Cyg has two solid-solid transitions and Cas three occurring at temperatures of 318'5, 3385 and 431 K as observed by Strobl er al (1974) and Ewen ef al (1974) who have determined the defect structure and molecular motions in the various modifications of this compound using x-ray, NR and infrared techniques. ‘The structure of @ Fischer-Tropsch medium wax is illustrated in figure 1 (Le Roux et al 1976). The extent of amorphous phase A, containing chain ends, is determined by the end group concentration which is about 7% for this wax. B represents ‘rigid amorphous zone or defects caused by branches. Medium wax contains an average of 24 branches pet 1000 earbon atoms, Zone C, the mobile amorphous zone, ‘mainly consists of the lowest melting iso-paraffins that end up between crystallites during crystallisation. These regions are filled by about 12% oil, consisting of @ mixture of ‘n-Cyy with the same average chain length of 28 carbon numbers, but branched to a much larger extent. The D zone, representing about 80% of the volume of the wax, closely resembles pure n-Czs, Like m-paraffins with odd 1m, this zone normally has an ortho- thombie structure below the phase transition,NMR investigation in Fischer-Tropsch waxes Figure 1. (a) Structure of a Fischer-Tropsch medium wax, The different zones are discussed in the text, (B) Regular areangoment of chains ina two-dimensional model of & ‘onary mixture of paraffins. (c)Iregular arrangement of chains inthe same two-dimen sional mode! 3. Experimental details Cas» was obtained from a Fischer-Tropsch wax by fractional distillation and crystal- Tisation. Cas is of medium hardness and is fairly brittle and non-adhesive, Tt has an isoparaffinie content of 1-2% and a crystallinity of 837%. Cces.s> was obtained by distil- lation from Cass. The carbon numbers of Ceas> and Ccas.s> ranged from 17 to 39 and 24 to 34 respectively, in approximately gaussian distributions. Sufficient oil (~1em9) was extracted from Ces, as it had become necessary to identify the contribu- tion to the spin-lattice relaxation time due to this source Second moments were found by numerical integration of the absorption curves obtained using a marginal Spin-Lock spectrometer operating at 30 MHz. Corrections for finite modulation amplitudes were made. The spin-lattice relaxation time measure- ments were determined using a 52 MHz Spin-Lock coherent-pulse spectrometer. The emperature at the sample, placed in a helium gas refrigerator, was controlled by a heater driven by a temperature regulator. A calibrated platinum resistance thermometer in contact with the sample was used to measure the temperature which could be main- tained t0 atleast £05 K. 4, Results 4.1, 1H Second moment Over the temperature range 110<'<200 K, the derivatives of the resonance line show no fine structure. Above 200 K, a narrow component, artificially broadened by the us.1966 JA J Lourens and EC Reynhardt Modulation field of ~1G, becomes prominent. This line, which has a peak-to-peak width of ~1-5 G, is attributed to the protons in the mobile amorphous phase of the wax (65). As the temperature increases the wide component gradually disappears leaving only A very narrow linc, characteristic of a liquid, at 334K, (The melting point of the wax is 332 K (Le Roux 1969a).) First derivative curves at some selected temperatures are shown in figure 2. Figure 2. A selection of Coan rst derivative eure. ‘The modulation fe! was 163 K; broken curves, 218 K; chain curves 278K. ‘The proton second moment is shown in figure 3 as a function of temperature over the range 110 192K) the two relaxation times exhibit In the solid phase (T'< 192 his occur at 865 K~!. From the linear depend- B for B>6:5K-, an activation energy of 1-1 40-1 keal/mole is obtained from both curves An example of © Nonexponential behaviour of the signal decays, The ated with the wax and oll fractions is alsoJAI Lourens and E C Reynhardt 1o007F 1") Figure 5, Temperature dependence of 71 of the pure oi sample. The 'H spin-lattice relaxation times of Ccas> and Ceans» isolated from the none exponential decays are shown as a function of temperature in igure 6, Relaxation times which did not coincide within experimental error with those obtained from the pure oil sample have been assigned to the protons in the respective waxes In Ceany a phase transition, manifested by an abrupt change of about 250 ms in T1 cceurs at B=3-63K-1 (T=275 XK), The slope of the best straight line through the experimental points below the transition yields an activation energy of 66 40-5 kcal 10077 1x4 Flguce 6. 7125 2 function of 1000/7 for m-Ces and the two waxes, AS, Cap values from ‘Anderson and Slicer (1965)vil NMR investigation in Fischer-Tropsch waxes 1969 AT minimuin of 90 & 10 ms oceurs at 2=3-46 K-1, On the high temperature side of the transition the slope corresponds to an activation energy of 122 kealfmole. Just below the melting point of the wax, T' starts to decrease rapidly, but no reliable value for this process could be obtained. Below the melting point of the oil (192 K), 71 (oil) is always less than T1 (wax). ‘Therefore only the long component of T: was measured. In this temperature region (> 45 K~!) the symmetrical arp curve with a minimum of 340: 20 ms at B=7-25 K-! yields an activation energy of 1-95+0-1 kcal/mole. The T1 against B curve for C2x.s), the wax having the smaller chain length disorder value (Ar=['81), is similar to the one obtained for Cyas, for which Ar=4-12, The structural transition occurs at a temperature of 301 K and the corresponding activation energies are somewhat larger, viz. 7:9:40-5 kcal/mole below and 1842 kcal/mole above the transition temperature. In the temperature region B>4°5 K-, the corresponding value is 213 £041 kealfmole. The spin-lattice relaxation measurements of Anderson and Slichter (1965) on the pure compound, mCas, have been extended to higher temperatures (B<4-5K~!), A new solid-solid transition has been observed at 317 K (figure 6). From the variation of 7; with 6(B-<4:5 K-}) just above and below this phase transition an activation energy of 10-641 keal/mole is obtained. In the low temperature region (>4-5 K-%) Anderson and Slichter (1965) reported an activation energy of 26 +0-2 kcal/mole and a 7 minimum of 215 ms at 8=638 K-!. The activation energies associated with the various molecular motions are summarised in table 1 and discussed in the next section, Table 1. Activation energies in kcal/mole associated withthe various molecular motions in Cos, Ceassy and Ces Obtained from the slopes above and below the transition temperature of 317K. 5. Discussion Since the appearance of the narrow component of the proton absorption curve coincides with the melting point of the oil contained in the waxes, itis concluded that the narrow line arises from the protons in the oil, ie. the liquid amorphous phase of the waxes, If the small change in second moment (~ 1-3 G4) at 210 K is attributed to the melting of the oll, it follows that approximately 10% of the protons form part of the oil. (The experi= mental Ma for the oil below the melting point is 12 G2) The total theoretical second moment of an 1-Cy, compound, assuming that the end methyl protons are reorienting sufficiently rapidly, has been calculated to be Me 26-3~65-7)(m+ 1) G? for an otherwise rigid system. For a perfectly rigid system the value is 26-34 19°1)(m-+ 1) G? (Andrew 1949). For 7-Csg the Ma values for a rigid lattice ‘and reorienting methyl groups therefore follow as 27 and 24 G2, As will be discussed later, the rigid lattice Mg exists only below 70 K, implying that the experimental second moments in Cgay and Cces.s» represent rigid n-paraffin chains with reorienting methyl ‘groups as well as a small contribution from the solid oil between 110 and 200 K. Above1970 JAS Lourens and EC Reynhardt 192 K, the melting point ofthe oil, its contributi mental value of 24 G? between 210 at from the waxes. methyl groups, In the absence of x-ray and related measurements on Cay an unambi fication of the motional mechanisms associated with the two-step decrease in the second ‘moment cannot at this stage be given, However, it seems likely, in view of the work of Andrew (1949) on 1-Cos, that of Olf and Petertin (1970a,b,c) on n+Cso and the extensive work of Ewen ef al (1974) on C3, that the first step-like reduction of about 8 G in Cos is caused by the s0 called “Tip-Aop” jumps—the molacules perform thermally fctivated rotational jumps through 180° between two equilibrium positions, each jump being accompanied by a simultaneous translation along the chain axis by one CHs group Itis possible that cooperative rotational jumps can also occur in n-Ces in addition to the flip-flop jumps. The motional mechanisim giving rise to the first reduction in Afs will be referred to as the reorientational-translational (Ret) mechani, According to the Ty relaxation measurements Cees) and Ccas.s> undergo structural phase transitions at 275 and 301 K respectively. Although it is obvious that the initial reduction in Mz of about 8 G? from 230 K up to these transition temperatures is caused by the Ret mechanism, the activation energies decrease from 10% kcal/mole for the pure compound to 7-9 and 6-6 keal/mole for Cass, and Ccas» respectively. This decrease in activation energy and transition temperature with increasing chain length disorder Ar can be qualitatively accounted for in terms of a simple, two-dimensional model of a binary mixture of paraffins as indicated in figure 1. Considering that the chains move in a Potential which mainly arises from the interaction between nearest-n interaction between a short chain and its nearest neighbours in figure 1(3) is I the corresponding interaction in the case of the irregular i the former case the transition tempera ion to Ms is practically zero, ‘The experi- 240 K therefore represents the true contribution is in exact agreement with the th for reorienting ]Ous speci- rwer than ment in figure I(e). In ature, which is caused by the onset of the Ret motions, may be expected to lie somewhat between the transition temperatures of the two individual components. In the case of the irregular arrangement of chains the transition femperature is expected to fall below the value corresponding to the shorter chains, as observed experimentally. Hence the it motions ina wax appear to be induced by the ‘more weakly coupled chains which have the smallest moment of inertia, The final rapid decrease of about 16 G?in Ms of -Czs is ascribed to a more continuous {css jump-like rotational motion accompanied by diffusion of intrachain dlefeets along the chain axes (Ewen ev al 1974). 1t is reasonably wel established that the transition to the hexagonal state in n-Cas, Caass> and Ceas> occurs a few degrees below their melting Points (ef. figure 7) (Stokhuyzen and Pistorius 1970). Although the rotational-diffusional ‘mechanism (Ron) sets in atthe transition temperature to the hexagonal state in n-Cas, this is certainly not the case in Cc2s.s» and C25» as revealed by the second-moment meacure ‘ments. The final reduction in the second moment of these waxes, which is attributed to the Rob mechanism, starts affeting Mz a few degrees above the transition temperatures, oF 301 and 275 K in Ccas.s> and C cen» respectively, while the transition to the hexagonal Stale occurs at 3262 K in both the waxes. ‘The waxes are therefore characterised by the onset of the nov motions close to structural phase transitions which are reduced Zelative tothe transition tothe hexagonal state. This result is of considerable technological Significance since such physical properties as hardness, density, thermal expansion and thermal conductivity are expected to be influenced by the oD motions. In the absence of Xray measurements a quantitative explanation of the transitions at 301 and 273 K ‘cannot be given on the basis of the Nox results alone. Below these transition temperatures the disec hon: the temp. of Si Coe of ac T temp. oun grou) active The « the m to act G Ande: betwe group Al aspect expla’ branc>ution, enting speci- seond rk of nsive nally jump up. >the be (ural ‘tial sed Ar fa the In ker as the the he val © NMR investigation in Fischer-Tropsch waxes Figure 7. A schematic representation of the structural phases nd chain motions in Com, Ceao and Css, The symbols M and HEX refer to monoclini and hexagonal structures respectively while O; and Os represent two orthorhombie phases, ‘The other symbols are diseussad in the tex. the waxes are assumed to be in an orthorhombic state. At the transition temperatures 2 discontinuous change in lattice dimensions takes place, presumably to a different ortho thombie state in which nop motions can conceivably occur. Similar to the RET motions, the Ron motions also appear to be induced by the more weakly coupled chains in the wanes, As an inereasing number of chains start executing kop motions with increasing temperature above the presumed orthorhombic-orthorhomibie phase transitions, the second moments decrease. Just above the transition to the hexagonal state al the chains cain execute ROD motions. According tothe differential scanning calorimetry endotherms of Stokhuyzen and Pistorius (1970) the transition to the hexagonal modification a few degrees below the melting point of the waxes is also fist order. In contrast to C.99 and Caan» the new solid-solid transition observed in n-Cap at 318 K does not mark the onset of a different molecular behaviour (figure 7). The spin-latice relaxation times of Ces, Cesss) and Cces> all display temperature dependence in the range 12> > 45 K-' (igure 6). Just as in Pounds the minima in the waxes are ascribed to the threefold reorientation ofthe methyl groups. In #-Cw all the minima occurred at 146 K (8=68 K-1) and the corresponding activation energy of 246402 keal/mole was found to be independent of chain length ‘The activation energies in the waxes (ef table 1) are about 25% smaller, a result which can once again be explained on the basis of structural diferenees, The average number of nearest-ncighbour hydrogen atoms surrounding a methyl group in the waxes is less than the umber surrounding a methyl group in r-Cy. Consequently less energy is required to activate a methyl threefold reorientation in the waxes Calculations show that in Cces.s) anid Ccas> as well as in all paraffins studied by Anderson and Slichter (1965) the frequency of the Cs reorientations is the same as the inverse of the linewidth between 60 and 70 K. Therefore all experimental second moments between 70 K and 240 K. correspond to a rigid chain with Cs reorientations of all methyl sroups. Although our attention was focused on the molecular motions in the waxes, a few aspects of the pure oil 7; results will be discussed, The non-exponentiality could be explained qualitatively in terms of a model in which the methyl groups belonging 10 branches and chain ends are not equally effective in relaxation to the lattice, Below the1972 JAS Lourens and EC Reynhardt melting point the relaxation results exhibit two minima at approximately the same femperatuce at which 71 minima were observed for Cs reorientations of methyl groups in separaffins. ‘The low activation energies (1-0: 01 keal|mole) reveal that owing to the high degree of branching the oil methyl groups have environments tat differ to a large extent from those of methyl groups in n-parafins, 6. Conclusions Whereas the solid-solid transition to the hexagonal phase in n-Cyx compounds with carbon number m around 28 marks the onset of Roo motions, these motions set im at temperatures of ~27K and ~50K below the transition to the hexagonal state in Ceagss and Cas, respective :00 motions is preceded by structural phase transitions which occur at temperatures depending on the range of carbon number Ar in each wax. The fact that rod motions do in fact take place ina Presumably orthorhombic phase is consistent with a model in which the chains are Facked in an irregular staggered arrangement in a wax. As the more weakly coupled chains start executing Rop motions at suitable frequencies in larger numbers with increasing temperature, the second moments are correspondingly affected axes the onset of the x Acknowledements We thank the South Aftiean Coal, Oil and Gas Corporation Lid for supply the samples and Dr JH Le Roux for helpful discussions References ‘Anderson JE and Slichter W'P 1965 J. Phys. Chem 69 3059 Andrew ER 1949 J. Cheri Ps, 18 667 Ewen B, Fisher EW, Piescack W and Strobl G 1974 J. Cem. Phys. 61 $2 Le Roux JH 196987. Appl. Chem. 199 = 19694. Appl Chem. 1986 — 1969 4. Arpt. Chem. 19 19704. Arp. Cher 20 203 Le Roux JH, Retief JJ and Pretorius § 1976 Jat. Syne. o Analyucal sity, Jol Le Roux JH, Smith RDF, Turner R and Weidema 1974 J. Appl. Chem. Biotecinol 2481 MeClure DW 1968 J. Cher, Piss. 49 1850 Miller A 1928 Proc. R. Soc. 120 435 — 1932 Proc, B Soc. 138314 Odgjima A, Sauer JA and Woodward AE 1962 J. Phys. Chem. 66 718 OM HG and Peteiin A 19703 J. Polymer Sel. A-2 8733 19100 J. Polymer Sei, A-28 71 — 19700 J Polymer Sc. A-2 8 791 Smith AE 1983 J Chem, Phys. 24 2229 ‘Stokhuyzen R and Pistorius CWET 1970 J, Appl Chem. 20 1 Strobl G, Ewen B, Fisher EW and Piescesk W 1974 J. Chem. Phys. 61 $257 ‘Templin PR 1963 Proc. ASTM-TAPPI Symp. on Ptroleun Waxes, New York (Now York: TAPP) pt (Chemises, Rael Afrikaans Univers