X-rays Diffraction from Fibres

Typical fibre X-ray diffraction pattern

Intensity curveEquatorial scan of A Nylon6 fibre

Crystallinity by X-rays

X-ray Diffractometer

Crystallinity by X-rays
Bragg s condition for diffraction: 2dsin = n

Crystallinity: Scattering from the sample = I(s) (s = 2sin / ) Scattering from the crystalline Part = Ic(s) Xc = 0 Ic(s)dxs / 0 I(s) dxs I(s) dxs = 4 0 s2 I(s) ds 0 (For spherical symmetry dxs = 4 s2 ds) Xc = 0 s2Ic(s) ds / 0 s2I(s) ds ------------------(1) Powered sample measurement Effect of voids no effect.

Crystallinity by X-rays
Crystallinity Index: Method for materials when 100% amorphous not available Standard Crystalline and amorphous samples: Cellulose:-c- hydrolysed in HCl, a- Alcohol extracted. (Iu Ia) = Cc(Ic Ia) + B

(Iu Ia)

Slope = Cc

Ic - Ia

X-ray intensity curves of the crystallinity and amorphous standard

X-ray intensity curves of the crystalline and amorphous standards used for the analysis of cotton cellulose.

X-ray intensity curves of the crystallinity and amorphous standard

The numerical values of Ic, Ia and Iu can be used to calculate an integral or a correlation crystallinity index. For either index the differential intensities Iu Ia and Ic Ia are first determined at all incremental points between the angular limits 2 o nad 2 m. The Integral index Ci is calculated with the expression: Ci=[2
o 2 m(I u

Ia)] / [2

m(I c

Ia)]

which is seen to be a measure of the area between the curves of Iu and Ia divided by the area between the curves of Ic and Ia. The correlation index is the slope of the straight line obtained on plotting Iu Ia versus Ic Ia for all the data points.

Crystal Sizes
Io

hkl diff. peak

Scherrer s Equation:
I

Size of the crystal: Lnkl =K / cos crystal defects also give rise to broadening Small angle Xray scattering for crystal sizes: 2dsin = n Pseudo Lattice with d ~ 100 Ao, = 0o Long Periodicity: d = C+A, X = C / (C+A)

C A

1.5

Small angle Xray scattering for crystal sizes:

Diffracted X rays

Xray sound Sample

Void Sizes

Guinier s Law lnI(s) = lnI(0) 1/3 s2 R2

lnI(s)

Slope = -1/3 R2

s2

SASX

Modulus of PE by X-ray diffraction

Highly oriented PE o d002 = 0.127nm 002 = 37.379 Stress of 1GN/m2, 002 = 37.226o Strain(?) 2 * 0.127(1 + )Sin(37.226) = 0.1542 = 1/285, Modulus = 1/(1/285) =285 Gn/m2

0.5

1.0

1.5

Xc = 0.60, = 1000 kg/m3, c = 855 kg/m3 = 0.15 nm Maximum At 2 of 0.5o Long Period is d 2dsin = n n=1 2*d sin(0.5/2) = .15nm d =~ 20 nm d= c+a X = c/(c+a) = 0.7 c=(c+a) * 0.7 = 20 * 0.7 = 14 nm

Schematic Presentation of various small angle patterns

Two point pattern:

Four point pattern:

Equatorial Pattern:

Typical Results from SAXS in Ao

PE Long Period Crystallite Length Amorphous Length Diameter 160 PP 90 60 30 120 90 Nylon 90 60 30 330-160 PET 150 180

Nylon 6 Fibres

PET Fibres

Nylon 6 Long Period 86, amorp = 28.7; N66 91Ao & 30.3 Ao

X-ray photographs of nylon fibres

Crystalline Orientation by X-ray diffraction

Preferred orientation Primary bonds for deformation. Presence of arcs in diffraction pattern Herman s Orientation function(Affine deformation): f = [3(cos2)-1] fc,z = [3(cos2 c,z)-1] fa+fb+fc = 0 For perfect orientation = 0,(cos2 ) = 1, f = 1 For random orientation (cos2) = 1/3, f = 0 For cylindrical symmetry (cos2) = [o /2 I()Sincos2 d] / [o /2 I()sin d] Experimental Measurement: Calculate f from the following data: I() = cos (cos2 ) = [o /2 Sin cos3 d] / [o /2 cossind] = o 1 x3 dx / o 1 x dx = x4 *2 / 4* x2 lo1 = [3/2 1] = 1/4

For uniaxial orientation, a series of (hkl) planes pref. Perpendicular to fibre direction. Polyethylene: (110);(200);(020) to determine fa and fb Orthorhombic(a = b = c) Polyethylene terephthalic lacks (h o o) or (o k o) reflections. (T, o , 5) off meridian reflection. Triclinic cos2 hkl = e2 cos2 n + f2 cos2 + g2 cos2 + 2ef cosa cosb +2fg cosb cos c + 2ge cosa cosb ..(1) e, f, g are geometric constants of the unit cells. In general cos2 hkl are required to determine fn(1) Polypropylene: (110) & (040) are used for fc

Monoclinic 2 = 14.2 2 =16.9 For PP < cos2 c, z > = 1-1.099 < cos2 110, z > -0.901 < cos2 040, z > For PET T05 reflection is used for fc determination.

For nylon < cos2 b, z > = 1.0-1.20 < cos2 200, z >-0.795 < cos2 202, z > Orientation in amorphous regions:oriented amorphous halo observed in the case of PET Biaxial orientation.

Small-angle diagram of linear polyethylene drawn to an extension ratio of approx.6:1 at 115oC.Nickel-filtered CuK radiation; specimen-to-film distance, 400mm fibre axis,b3

Relationship between the length of the meridian streak and the transverse dimension of the diffraction source.

The decomposition of the diffraction pattern for polypropylene.

Plot of Iu Ia versus Ic Ia for a typical cotton sample

Relaxation time distribution controlling the width of loss peak and length distributions are related to long peak.