Physical and tensile testing and nanocomposites

BBE 4404 Lab 3 and 4 Report

Kristina Coster , Isaac Davy , Raphael Palucci Rosa3, Olas Rooker4, Lenilton Vidal Agostinho5
December 8th, 2015
1

Introduction5
Cellulose is the main component of wood and the most common organic polymer. Cellulose is
composed by glucopyranose monomers connected through -1-4 bonds. Each glucopyranose
contains three free hydroxyl groups, which are able to form hydrogen bonds with other polymer
chains (or with itself), giving rise to its major physical properties.
Nanocelulose is nano-sized cellulose (cellulose nanofibers), and its high mechanical performance
has attracted significant scientific attention over the past years. As a result, it is expected that the
addition of nanocellulose to another polymer matrix may provide positive reinforcement,
creating strong nanocomposites (polymer matrix and nanoelements) that can be used in a large
number of new applications.
Having this in mind, this experiment aimed to certify and justify changes in tensile properties of
nanocellulose-PVA nanocomposites in relation to neat PVA according to ASTM D882.
Nanocellulose-reinforced PVA composite films were prepared and tensile tested. In addition, two
different kinds of PVA (99% and 87-89% hydrolyzed) were intentionally used so that different
nanocellulose-PVA interactions could be analyzed.
Methods5
Nanocellulose reinforced PVA composite films preparation.
Two different nanocellulose concentrations needed to be analyzed (0% and 8%) by the group.
Once two different kinds of PVA (99% and 87-89% hydr.) were used to prepare previously the
PVA water solutions (6g of PVA and 500mL of water), there were a total of four different
solutions.
Solution
1
2
3
4

Kind of PVA
99%
87-89%
99%
87-89%

Concentration of nanocellulose (%)

0
0
8
8

Table 1: PVA-nanocellulose composites assigned

Mass values were calculated for each solution, and are shown on the following table.
Solution
Kind of PVA
Mass of nanocellulose (g)
Mass of PVA solution (g)
1
99%
0
50.6
2
87-89%
0
50.6
3
99%
2.51
46.0
4
87-89%
2.51
46.0
Table 2: Calculated mass of each material to make composite

In the following table, the amounts massed to make each composite are listed. Notice that the
values vary a little bit if compared to the ideal ones for each concentration. This is due to human
error (from pouring).
Solution
1
2
3
4

Kind of PVA
99%
87-89%
99%
87-89%

Mass of nanocellulose (g)

0
0
2.548
2.549

Mass of PVA solution (g)

50.6
50.6
46.1
46.0

Table 3: Measured amounts of each component added to composite

To simplify the explanation, the preparation process of the solution 3 is going to be used as an
example. Notice that the process was repeated to all of the solutions.
In a scale, 46.1g of the PVA water solution were added to a colonial flask. Then, 2.548g of
nanocellulose were added to the same flask. After that, the mixture was stirred for 30 minutes
before being poured into a Teflon dish. The dish containing the solution was left at room
temperature, where it rested for 72 hours until the total solvent (water) evaporation, living a
nanocellulose-PVA film, which was posteriorly removed and tensile tested. The same process
was repeated for all the other three solutions.
In a future experiment, some ideas will be taken in order to avoid errors. For example, the same
person will be in charge of pouring all the solutions. This will standardize errors, whats good,
chemiometrically speaking. Another idea is lowering the temperature. Lower temperature will
avoid errors due to solution evaporation.
Tensile testing of nanocellulose-PVA plastic/composite films.
The previously prepared films were punched using a clipper. From each film, a total of three strip
specimens were cut (total of 12 strip specimens). Each strip specimen was divided in three
different regions (bottom, middle, top). After that, each region had its thickness calculated. The
average thickness was used during the tensile testing.
After adding all the thickness values in the tensile tester software, each strip specimen was
strained to failure (initial span of 1 inch at a rate of 5 inches per minute). All the data collected
are used to calculate the desired mechanical properties. In the end of the process the weight of
each broken specimen was recorded, and then carried to the oven, where it was dried until
moisture free, so that moisture content and specific gravity could be obtained.

Result of experiments4
Matrix
Polymer
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
AVERAGE
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
AVERAGE
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
AVERAGE
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
PVA 99+% hydr.
AVERAGE
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
AVERAGE
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
AVERAGE
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
AVERAGE
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
PVA 87-89% hydr.
AVERAGE

Fiber mass
Fraction (%)
0
0
0
0
0
4
4
4
4
4
8
8
8
8
8
16
16
16
16
16
0
0
0
0
0
4
4
4
4
4
8
8
8
8
8
16
16
16
16
16

Replicate
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4

Modulus
(GPa)
1.55
1.53
1.73
2.32
1.78
2.37
2.28
2.32
2.23
2.30
2.32
2.08
2.14
2.39
2.23
2.18
2.29
2.78
3.01
2.56
1.88
1.74
2.12
1.61
1.84
1.73
1.44
1.80
1.98
1.74
2.51
2.90
2.17
1.98
2.39
2.57
2.60
2.76
2.66
2.65

Table 4: A summary of all strength properties of the polymers tested in this lab.

Strength
(MPa)
54.5
45.0
35.7
45.07
50.2
48.8
54.9
52.0
51.45
53.3
50.9
53.5
52.54
66.4
67.9
66.5
66.94
53.5
43.6
52.2
41.5
47.7
46.7
51.7
52.0
50.12
55.7
61.2
55.7
57.2
57.41
64.7
66.7
70.7
72.1
68.55

Strain
at
MC (%)
break of tensile
(%)
specimen
181
12.2
90
4.7
51
9.8
214
10.0
134.21
9.15
21
15.6
59
6.3
37
8.9
100
4.5
54.38
8.81
20
2.0
34
0.0
16
6.7
55
7.7
31.31
4.10
14
7.8
6
5.0
24
5.9
16
10.0
15.07
7.17
224
-2.6
90
8.1
233
10.3
82
5.0
156.9
5.2
61
22.4
110
8.2
10
0.0
14
8.5
48.87
9.78
8
7.0
14
5.3
17
8.3
16
4.4
13.69
6.25
19
2.3
18
5.1
5
9.3
10
8.0
13.04
6.18

99% PVA-0% NC
40
35
30
25

Stress (MPa)

20
15
10
5
0
-5

0.1

0.2

0.3

0.4

0.5

0.6

Strain (in/in)

The data collected for this lab varied greatly across the experimental process as seen in Table 4
above, however it is still possible to draw conclusions regarding how the mass fraction of
nanocrystalline cellulose added to a matrix of PVA affects the overall properties and
characteristics of the final polymer. The table shows that, in most instances, increasing the mass
fraction of nanocrystalline cellulose lead to an increase in the modulus, thus describing a
polymer more resistant to deformation and straining (Figures 1 and 2).

99% PVA-8% NC
60
50
40

Stress (MPa)

30
20
10
0

0.02

0.04

0.06

0.08

0.1

0.12

-10

Strain (in/in)

Figure 1: Stress/strain curve of 99% PVA with 0% nanocrystalline cellulose added.

Figure 2: Stress/strain curve of 99% PVA with 8% nanocrystalline cellulose added.

0.14

0.16

0.18

Comparing the slopes of in the figures above, it is not clear which sample is stiffer since the
scales of the x-axes are not equal. Adjusting the 0% scale to reflect that of the 8% NC addition
sample, it is easier to see the contrast between the two moduli.

Adjusted Scale

99%-8%

0.02

0.04

0.06

99%-0%

0.08

0.1

0.12

0.14

0.16

Strain (in/in)

Figure 3: Stress/strain curve of 99% PVA with 8% nanocrystalline cellulose and 99% PVA with 0% NC on adjusted x-axis.

Noting that the 8% NC addition lead to a much steeper slope between 0% and 2% of strain, it is
clear that the NC created a stiffer polymer over the original PVA with no nanocellulose (NC).
This also means that 8% mass fraction NC increased the modulus of the polymer leading to a
better resistance to deformation in 99% PVA with NC addition. This is expected since the
addition of NC theoretically adds strength to the polymer, providing more structure when
random, nonuniform fibers are present. The same relationships were noted in 87-89% PVA,
however the scatter in the data and the expected result of increased modulus with each increase
in NC mass fraction was not always the outcome. It is not clear if moisture content was a factor
that affected modulus in individual samples since the spread of percent moisture compared to
observed modulus was not a proportional relationship (Table 4).
Related to modulus, it can be easily seen from observing the y-axes in Figures 1 and 2 that the
strength of the polymer also increased with higher NC mass fractions. And while the scatter of
the data was high in modulus comparisons, that same observation does not carry over to describe
strength; there is a clear rise in maximum strength with increased NC addition for all addition
levels in both 99% and 87-89% PVA (Table 4).
The scale of the x-axis had to be adjusted in order to compare the moduli of the samples
described above because the observed strain at break changes dramatically with each increase in
NC addition. Comparing Figures 1 and 2, the flexibility of the polymer decreases rapidly with
an increase in mass fraction of NC. This relationship can be observed in Figure 6 where the
strain at break data is plotted to show a decreasing trend.

Below are scatter plots describing the spread of data for the modulus, strength, and strain at
break for 99% PVA at 87-89% PVA for each NC addition level. The same data is presented in
Table 4.

Modulus
3.00
2.80
2.60
2.40
2.20

Modulus
Average Modulus
(GPa)

2.00
99%

Modulus 87-89%

1.80
1.60
1.40
1.20
1.00
-0.5

1.5

3.5

5.5

7.5

9.5

11.5 13.5 15.5 17.5

Fiber mass fraction

Figure 4: Modulus data scatter with error bars for 99% and 87-89% PVA polymers with NC addition at 0%, 4%, 8%, and 16%.

Strength
70.00
65.00
60.00
55.00

Strength 99%
Average Strength (MPa)

Strength 87-89%

50.00
45.00
40.00

35.00
-0.5

1.5

3.5

5.5

7.5

9.5

11.5

13.5

15.5

17.5

Fiber Mass Fraction

Figure 5: Strength data scatter with error bars for 99% and 87-89% PVA polymers with NC addition at 0%, 4%, 8%, and 16%.

Strain at Break
180.00
160.00
140.00
120.00
100.00

Break 99%
Strain at BreakStrain
(%) at80.00

Strain at Break 87-89%

60.00
40.00
20.00
0.00

10

12

14

16

18

Fiber mass fraction

Figure 6: Strain at break data scatter with error bars for 99% and 87-89% PVA polymers with NC addition at 0%, 4%, 8%, and
16%.

Discussions3
The effects of adding cellulose nanofiber in PVA compounds are an increase of the Modulus
(GPa) and Strength (MPa) of the materials. According with the data collected in the experiment,
we can observe that the average of these two proprieties increased as the amount of nanofiber
were added. These values can be observed in the Table 5 below.
Matrix
polymer
PVA 99+
%

PVA 87+
%

Modulus
(GPa)

Increased
%

Strength
(MPa)

Increased
%

1,78
2,30
2,23
2,56
1,84
1,74
2,39
2,65

29,07
25,23
43,89
-5,41
30,03
44,13

49,36
51,45
55,27
63,02
47,70
48,06
57,41
68,55

4,24
11,98
27,67
0,75
20,35
43,69

Strain at
break
(%)
134,21
54,38
31,31
15,07
156,90
48,87
13,69
13,04

Decreased
%
59,47
76,67
88,77
68,85
71,99
4,73

Table 5: Mechanical proprieties changes with addition of cellulose

In addition the strain at break was the only propriety of these three that had a decrease as the
cellulose were added in the compound. This happened because as we mixed the polymer with the
cellulose the flexibility increased, but the strain is inversely proportional to the strain.

Modeling1,2

Tensile stiffness of nanocellulose composites

4.5
4
3.5
3
2.5
(calculated)
ModulusEc
(GPa)

Linear (Ec (calculated) )

Ec (experimental)

Linear (Ec

1.5
1
0.5
0

10

12

Fiber Weight Fraction (%)

Figure 7: Calculated and experimental moduli of nanocellulose composites of various weight fractions

The tensile stiffness values of nanocellulose composites of 99% hydrolyzed PVA were calculated
using the given moduli, aspect ratio, and density of the fiber, and the density and modulus of the
matrix, which were calculated from the 0% nanocellulose composites averaged specific gravities
and moduli of elasticity, respectively.
The volume fraction of the fiber composite was calculated using the following:
W f f
=
V f c
Where Wf =weight fraction of the fiber
Vf= volume fraction of the fiber
= density of the fiber (f) or composite (c), respectively

(1)

14

Using that information, Halpin-tsai relations were used to calculate E1 and E2

For E1: =2aspect ratio
(2)
For E2:

=2+ 40 V 10
f

(3)

Ef
1
Em

(4)

Ef
+
Em

( )

And then E1 and E2 were calculated using the following:

1+ V f
E=E m
1V f

(5)

The composite modulus was then calculated using

3
5
E c = E 1+ E2
8
8

(6)

This was done for nanocellulose inclusion rates of 0, 4, 8 and 16 percent. The calculated moduli
can be seen compared to the experimental values in Figure 7 above. All calculated values and
intermediates can be found in the attached appendix and in the excel file BBE4404 Lab Data
Group 2a
Ec (calculated) (GPa)
1.78
2.12
2.48
3.27

Ec (experimental)
(GPa)
1.78
2.30
2.23
2.56

Deviations
(GPa)
0.00
0.18
0.25
0.71

Deviations (%)
0.00
7.66
11.32
27.57

Table 6: Deviations in calculated and experimental moduli.

As shown in Table 6 above, there was a slight observed deviation between the experimental
values and the calculated values, which increased as the fiber weight fraction increased. One
reason for this could be because in order to calculate the modulus for these composites, we had
to initially assume that the fiber in the composite was uni-directionally aligned and
discontinuous. We then corrected for this using Equation (6) but it may not be as accurate.
Additionally, the experimental data may be off due to human error.
Conclusions and recommendation for future studies1
This lab compared the strength and tensile properties of PVA-nanocellulose composites. It was
observed that composites with a greater percentage of nanocellulose displayed greater values for
both the moduli and strength. It was also observed that the PVA that was hydrolyzed to a lesser
extent also displayed higher moduli and strength values. This indicates that composites made

with PVA that is not fully hydrolyzed and high amounts of nanocellulose are the strongest of the
composites tested.
Though the modeling was only done for composites with 99% hydrolyzed PVA, the same
assumptions can be made. There was a noticeable difference in the calculated moduli of the
composites, especially at higher nanocellulose inclusion rates, which shows that these
composites can be unpredictable.
In order to get more accurate results, it is recommended that more samples are taken and
analyzed for each composite. This would be helpful in determining outliers in data that may have
a significant impact on the average of the data set and thus affecting preceding calculations.
More care would also be taken throughout the lab as a whole to insure that human error is
minimized.

References
Lani, N., Ngadi, N., Johari, A., & Jusoh, M. (n.d.). Isolation, Characterization, and Application
of Nanocellulose from Oil Palm Empty Fruit Bunch Fiber as Nanocomposites. Journal of
Nanomaterials, 1-9. Retrieved December 5, 2015, from
http://www.hindawi.com/journals/jnm/2014/702538/
Lee, S., Mohan, D., Kang, I., Doh, G., Lee, S., & Han, S. (n.d.). Nanocellulose reinforced PVA
composite films: Effects of acid treatment and filler loading. Fibers Polym Fibers and
Polymers, 77-82. Retrieved December 5, 2015, from
http://link.springer.com/article/10.1007/s12221-009-0077-x
Zhou, Y. (2012). Effect of nanocellulose isolation techniques on the formation of reinforced
poly(vinyl alcohol) nanocomposite films. Expresspolymlett Express Polymer Letters,
794-804. Retrieved December 5, 2015, from
http://www.expresspolymlett.com/articles/EPL-0003461_article.pdf

All work was completed together, however sections that individuals predominantly worked on
are indicated by the superscript number on each section heading. Corresponding names and
numbers are as follows:
Kristina Coster- 1
Isaac Davy- 2
Raphael Palucci Rosa- 3
Olas Rooker- 4
Lenilton Vidal Agostinho- 5

Appendix
Calculated intermediates and values for Modeling section