Results and Discussion

4.4 Nano Ca3(PO4)2: PA Composites

4.4.1 Physical properties of nano Ca3(PO4)2: PA composites

4.4.1.1 Hardness of nano Ca3(PO4)2: PA composites

Fig 4.30 The effect of weight percentage of filler loading (nano and commercial

Ca3(PO4)2 on hardness of polyamide composites. It is observed that hardness of

nano Ca3(PO4)2 filled polyamide nanocomposites is higher than that of commercial

Ca3(PO4)2 filled polyamide composites. Also the hardness of 11 nm Ca 3(PO4)2

found to be more improved than that of 23 and 17 nm sizes of Ca 3(PO4)2. The

hardness is recorded as 86 and 77 for 1 wt % loading of 11 nm and commercial

Ca3(PO4)2 respectively, while 4 wt % loadings of 11 nm and commercial Ca3(PO4)2

showed hardness 98 and 82 respectively. This might be due to uniform dispersion

of nano Ca3(PO4)2, which makes the surface of the composite hard and tough.

The improvement in hardness of polyamide composites is evidenced from the

results of elongation at break of polyamide composites [8-13].

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 98
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Fig 4.30: Hardness of PA filled with different fillers

4.4.2 Thermal properties of nano Ca3(PO4)2: PA composites

4.4.2.1 Thermal gravimetric analysis of nano Ca3(PO4)2: PA composites

Fig 4.31 to 4.33 shows thermal properties of pristine, commercial Ca3(PO4)2 and

nano Ca3(PO4)2 (23, 17, and 11 nm) filled polyamide composites. The

incorporation of, nano Ca3(PO4)2 into polyamide composites with reduced particle

size shows better thermal stability than that of commercial Ca3(PO4)2 filled

polyamide composite. 23, 17, 11 nm Ca3(PO4)2 shows decomposition temperature

at 500, 520, and 542 oC at 1 wt % loading, while 4 wt % loading shows

decomposition temperatures 543, 557 and 570o C respectively. The enhancement

in thermal stability is due to uniform dispersion and reduced particle size of nano

Ca3(PO4)2, which is responsible for the uniform absorption of heat and prevent out

diffusion of volatile decomposition products. It can be summarized from the results

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 99
 Results and Discussion

that the reduced nanosizes of Ca3(PO4)2 provides better thermal, and mechanical

properties than that of commercial Ca3(PO4)2 in polyamide- 6, 6. It can also be

observed from a morphological study that the nanoparticles dispersed uniformly

throughout the matrix up to a 4-wt % loading. As the uniform dispersion of nano-

Ca3(PO4)2 brings the chains closer and keeps them intact with nanoparticles and

provides more strength and toughness to composites than commercial Ca3(PO4)2 ,

whereas reduced nanosizes showed more enhancement in the hardness in

comparison to commercial Ca3(PO4)2. This is also due to the uniform dispersion of

the nanoparticles in the polymer chains [10-11]. As the nanoparticles are so small

that they dispersed uniformly in the matrix and intercalate polymer chains to

provide them with order i.e. orientation of molecules is taking place. However, the

amount of loading of nano- Ca3(PO4)2 causes decrement in elongation at break

this decrement in elongation at break is not due to agglomeration of nanoparticles

but due to catastrophic failure to the specimen with crack propagation, and thus

decreases the extensibility of the composite.

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 100
 Results and Discussion

Fig 4.31 TGA of 11 nm Ca3(PO4)2 polyamide filled with various sizes of

CaSO4

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 Results and Discussion

Fig 4.32 TGA of 17 nm Ca3(PO4)2 polyamide filled with various sizes of

CaSO4

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 102
 Results and Discussion

Fig 4.33 TGA of 21 nm Ca3(PO4)2 polyamide filled with various sizes of

CaSO4

4.4.2.2 Flammability of nano Ca3(PO4)2: PA composites

The rates of flame retardency of different filler compositions are shown in fig 4.34.

The nanosize Ca3(PO4)2 filled in polyamide shows significant improvement

flammability compared to that of commercial Ca3(PO4)2 filled polyamide. The

flammability values are 3.4 and 2.5 sec/mm for 1 wt % of 11 nm size Ca3(PO4)2

and commercial Ca3(PO4)2 respectively. It means, reduction in nanosize shows

better improvement in flame retarding properties. This might be due to the nano

filler, which creates the effective char layer on the surface, and it absorbs the heat

of burning (endothermic). In addition, Ca3(PO4)2 can delay the time before ignition

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 Results and Discussion

and suppress the release of smoke. Ca3(PO4)2 with high activity can also absorb

many substances, including free radical and carbon[8-11].

Fig 4.34: Rate of flame retardancy of PA filled with different fillers

4.4.2.3 Vicat softening temperature of nano Ca3(PO4)2: PA composites

The nano size Ca3(PO4)2 filled in polyamide shows significant improvement in

vicat softening temperature compared to that of commercial Ca3(PO4)2 filled

polyamide composite shown in fig 4.35. The vicat softening temperatures are 304

and 247o C for 1 wt % of 11 nm size Ca3(PO4)2 and commercial Ca3(PO4)2

respectively. It means that reduction in nano sizes shows better enhancement in

vicat softening temperature of polyamide composites [11]. it absorbs heat

uniformly. Uniform transfer of heat throughout the polymer matrix that makes the

surface hard and

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 104
 Results and Discussion

rigid.

Fig 4.35 VST of PA filled with different Nanofillers

4.4.3 Mechanical properties of nano Ca3(PO4)2: PA composites

4.4.3.1 Tensile strength of nano Ca3(PO4)2: PA composites

A relation between weight percentage of filler loading (nano and commercial

Ca3(PO4)2 and tensile strength of polyamide composites is shown in fig 4.38. It

is observed that tensile strength of nano Ca3(PO4)2 filled polyamide

nanocomposites is higher than that of commercial Ca3 (PO4)2 filled polyamide

composites [13]. Also the tensile strength of 11 nm Ca3 (PO4)2 is found to be

more improved than that of 23 and 17 nm sizes of Ca3(PO4)2 . The tensile

strength is recorded as 109 MPa and 96 MPa for 1 wt % loading of 11 nm and

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 105
 Results and Discussion

commercial Ca3(PO4)2 respectively. Whereas, 4 wt % loading of 11 nm and

commercial Ca3(PO4)2 shows tensile strength 102 MPa and 139 MPa

respectively. It means nano filler provides higher tensile strength compared to

commercial Ca3(PO4)2. This increment in tensile strength is due to uniform

dispersion of nano filler throughout the matrix [8, 10, and 11]. Also due to

reduction in particles size of Ca3 (PO4)2, that forms smaller spherullits for shorter

period of time. Moreover, during processing, rate of transfer of heat is uniform

from particle to particle due to fine sizes of nano Ca3(PO4)2 , which leads in

formation of composite without any failure .The uniform dispersion of nano Ca3

(PO4)2 is evidenced from AFM images as shown in fig10 (a-b). During tensile

test the fine cracks are developed on specimen shown in AFM photograph (fig

4.36 and 4.37).

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 106
 Results and Discussion

Fig 4.36 AFM Photograph showing Crack and Filler Dispersion in PA 66 - 11

nm Ca3(PO4)2 Nanocomposite

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 Results and Discussion

Fig 4.37 AFM 3D Photograph showing Crack and Filler Dispersion in PA 66 –

11 nm Ca3(PO4)2 Nanocomposite

Fig 4.38: Tensile strength of PA filled with different fillers

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 Results and Discussion

4.4.3.2 Young’s modulus of nano Ca3(PO4)2: PA composites

A relation between weight percentage of filler loading (nano and

commercial Ca3

(PO4)2) and Young’s modulus of polyamide composites is shown in fig

4.39. It is observed that Young’s modulus of nano Ca3(PO4)2 filled

polyamide nanocomposites was higher than that of commercial Ca3

(PO4)2 filled polyamide

composites. Also, the Young’s modulus of 11 nm Ca3 (PO4)2 is found to

be more than that of 23 and 17 nm sizes of Ca3 (PO4)2. 1 wt % loading

of, 11 nm Ca3 (PO4)2 shows Young’s modulus 3806 Mpa, while the same

wt % of loading of commercial Ca3 (PO4)2 Yields 3652 Mpa. Whereas, 4

wt % loadings of 11 nm Ca3 (PO4)2 and commercial Ca3 (PO4)2 show

Young’s modulus 4006 Mpa and 3727 Mpa.

Fig-4.39: Young’s Modulus of PA filled with different fillers

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 Results and Discussion

4.4.3.3 Elongation at break of nano Ca3(PO4)2: PA composites

Fig 4.40 shows elongation at break of polyamide nanocomposites with varying wt

% loading. It was found that with increase in weight percentage of filler loading,

elongation at break decreased. There was a continuous decrement in elongation

at break with increase in amount of filler loading for all compositions. 11 nm

Ca3(PO4)2 filled polyamide composite showed more decrement in elongation at

break compared to other nano sizes of Ca3 (PO4)2. This might be due to hard

nature of polyamide as well as nano inorganic filler. 1 % loading of nano Ca3

(PO4)2 showed elongation at break 20, 18, 16 and 14 % for commercial,

23,17and 11 nm Ca3 (PO4)2 respectively. Whereas, 4 wt % loadings of

commercial, 23,17, and 11 nm Ca3 (PO4)2 showed elongation at break 15,13,

10 and 8 % respectively. Addition of filler decreases the elongation at break of

composites. This is due to the increment in spherullits formation with reduction in

size and increase in percentage of filler. Moreover it provides catastrophic failure

to the specimen with crack propagation, and thus decreases the extensibility of

the composite [13].

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 Results and Discussion

Fig 4.40 Elongation at break of PA filled with different fillers

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 111