Crystallinity density measurement

Density, mechanical, and thermal properties are significantly affected by the degree of crystallinity. These properties can be used to experimentally estimate the percent crystallinity, although no measure is completely adequate (48). The crystalline density of PET can be calculated theoretically from the crystalline stmcture to be 1.455 g/cm. The density of amorphous PET is estimated to be 1.33 g/cm as determined experimentally using rapidly quenched polymer. Assuming the fiber is composed of only perfect crystals or amorphous material, the percent crystallinity can be estimated and correlated to other properties. 

Density. Density of LLDPE is measured by flotation in density gradient columns according to ASTM D1505-85. The most often used Hquid system is 2-propanol—water, which provides a density range of 0.79—1.00 g/cm. This technique is simple but requires over 50 hours for a precise measurement. The correlation between density (d) and crystallinity (CR) is given hy Ijd = CRj + (1 — Ci ) / d, where the density of the crystalline phase, ify, is 1.00 g/cm and the density of the amorphous phase, is 0.852—0.862 g/cm. Ultrasonic methods (Tecrad Company) and soHd-state nmr methods (Auburn International, Rheometrics) have been developed for crystallinity and density measurements of LLDPE resins both in pelletized and granular forms. 

Polypropylene molecules repeatedly fold upon themselves to form lamellae, the sizes of which ate a function of the crystallisa tion conditions. Higher degrees of order are obtained upon formation of crystalline aggregates, or spheruHtes. The presence of a central crystallisation nucleus from which the lamellae radiate is clearly evident in these stmctures. Observations using cross-polarized light illustrates the characteristic Maltese cross model (Fig. 2b). The optical and mechanical properties ate a function of the size and number of spheruHtes and can be modified by nucleating agents. Crystallinity can also be inferred from thermal analysis (28) and density measurements (29). 

The value for the heat of fusion of PPS, extrapolated to a hypothetical 100% crystalline state, is not agreed upon in the literature. Reported values range from approximately 80 J/g (19 cal/g) (36,96,101) to 146 J/g (35 cal/g) (102), with one intermediate value of 105 J/g (25 cal/g) (20). The lower value, 80 J/g, was originally measured by thermal analysis and then correlated with a measure of crystallinity deterrnined by x-ray diffraction (36). The value of 146 J/g was deterrnined independendy on uniaxiaHy oriented PPS film samples by thermal analysis, density measurement via density-gradient column, and the use of a calculated density for 100% crystalline PPS to arrive at a heat of fusion for 100% crystalline PPS (102). The value of 105 J/g was obtained by measuring the heats of fusion of weU-characterized linear oligomers of PPS and extrapolation to infinite molecular weight. 

Crystallization and Melting Point. The abihty of PVA to crystallize is the single most important physical property of PVA as it controls water solubiUty, water sensitivity, tensile strength, oxygen barrier properties, and thermoplastic properties. Thus, this feature has been and continues to be a focal point of academic and industrial research (9—50). The degree of crystallinity as measured by x-ray diffraction can be directly correlated to the density of the material or the swelling characteristic of the insoluble part (Fig. 2). 

Rossiter (1986) demonstrated the procedure for the production process of crystalline common salt from brine. It was found that the optimal median size is determined by the entrainment limit in the crystallizer. The crystallizer had to be operated at maximum allowable temperature and the slurry density measured for quality constraints. It was also suggested that cost discontinuities should be imposed based on temperatures of the available heat sources, possible materials of construction and other intrinsic properties of the system. 

Commercial low density polyethylene films were used (M 60,000 p = 0.920 g/ml 55% crystallinity as measured by x-ray... 

Figure 4 Plot of degree of crystallinity (XDSC) from DSC against crystallinity (Xp) determined by density measurements. (A), hydrogenated polybutadienes ( ), ethylene 1-butene copolymers ( ), ethylene 1-octene copolymers. Reprinted with permission from Ref. [72]. Copyright 1984 American Chemical Society. 

Jackson and McDonald13 analyzed samples of inulin from various sources. They obtained a uniform product by recrystallization from water, irrespective of the source. Since they determined total solids by refractive index and density measurements on the hydrolyzed inulin, they were not concerned with its crystalline form nor with its moisture content. 

Density measurements have been correlated to a number of physical properties. The crystallinity and purity of powders have been investigated using a variety... 

Note 4 The degree of crystallinity can be determined by several experimental techniques among the most commonly used are (i) X-ray diffraction, (ii) calorimetry, (iii) density measurements, and (iv) infrared spectroscopy (IR). Imperfections in crystals are not easily distinguished from the amorphous phase. Also, the various techniques may be affected to different extents by imperfections and interfacial effects. Flence, some disagreement among the results of quantitative measurements of crystallinity by different methods is frequently encountered. 

Figure 8 shows the relationship between the mass fraction wb of the broad component and the crystallinity (1 —X)[Pg.151]

The distinction between AHf and AHf has not always been borne in mind. Thus to determine AHf from calorimetric measurements it is necessary to know wc. The fraction of crystallinity can be estimated from density measurements through the equation... 

A routine method for determining relative crystallinity based on the amorphous bands in the spectrum has proved more rapid and precise than the x-ray method. In practice, the ratio of the 778 cm-1 (12.85 ft) and 2367 cm-1 (4.22 ft) band intensities is measured. Use of a ratio eliminates the thickness measurement and increases precision to about 1% at 50% crystallinity and considerably better at higher levels. A density measurement and an infrared crystallinity determination when combined give an estimate of the fraction of microvoids which can occur in molded specimens of polytetrafluoroethylene. The density of a sample is predicted on the basis of its crystallinity as measured by the infrared method and the difference between this density and the actual density measured by displacement in water is a measure of the microvoid content. This determination is precise to about 0,2% voids by volume. By the use of confirmatory infrared measurements, it is possible to check the possibility that the presence of a substantial percentage of voids may have led to erroneous indications of the molecular weight in the standard specific gravity test discussed earlier. 

As can be seen, for both samples the crystalline mass fraction (orthorhombic plus monoclinic) agrees well with that estimated from the density measurements and broad-line H NMR analysis. The thicknesses of the interphases are 3.8 and... 

Infrared spectroscopic methods are extensively used to analyse polymers due to their simplicity, rapidity, reproducibility, non-destructive character and ease of sample preparation. Degree of crystallinity [73], chain branching [74], degree of oxidation [75], density measurements [76], quantification of additives [75, 77], end-group analysis [78, 79] and other physical/chemical properties have been studied using MIR and/or NIR. 

Density of Steam Deactivated vs. Fresh Catalyst. The results of density measurements on the fresh parent of Catalyst A and on a portion of this catalyst that has been steam deactivated at 815°C for five hours (Table VIII) indicate a direct connection between the loss of crystalline microporous zeolite and increase in catalyst density. The major portion (67%) of the fresh catalyst is found in the density range 2.330 < d < 2.355 g/cc. By contrast, the major portion (87%) of the steam deactivated catalyst is found in the density range 2.372 to 2.394 g/cc. 

Figure 3. Crystallinities of several melt-processed and annealed-virgin PTFE samples as determined from decomposition of chemical shift lineshapes vj. crystallinities determined from density measurements...

The authors would like to thank Sam Gnaniah for determining the level of crystallinity within the polycaprolactone and Adam Calver for performing many of the density measurements. This work was funded by the United Kingdom Department of Trade and Industry as part of its programme of reseach on Materials for Processing and Performance (Project MPP 4.2 Physical Characterisation of Tissue Scaffolds). 

Litt, M. PoIy(4-methyl Pentene) X-ray measurement of crystalline density and observation of structural anomaly. T. Polymer Sci. A1, 2219—2224 (1963). 

---