1. The document describes a study to enhance the strength of paper using cellulose nanomaterials (CNF) and starch nanoparticles. CNF was derived from both hardwood and softwood, and was modified using glycidyltrimethylammonium chloride to impart a positive charge. Starch nanoparticles used were Ecosphere 2777. 2. Handsheets were formed from pulp, CNF, and additives using a standardized procedure. Physical testing showed that adding 5-10% CNF-GTMAC or 10% CNF-g-pAPTAC increased the dry and wet tensile strength of paper by over 20% compared to untreated pulp.

1. 1
Performance Enhanced Pulp by
Cellulose Nanomaterials
Eugenia Chan, Jeremy Kim
Mentor: Dr. Yao
http://www.mseco.com/wp-content/uploads/2014/07/paper_large.jpg

2. Purpose
• Collaboration with Ecosynthetix
• Renewable chemicals company with a focus on alternatives
to petroleum-based products
• Goal
• Enhance paper’s dry and wet tensile strength using
cellulose nanomaterials (CNF) and starch nanoparticles
(Ecosphere) on the order of 20% greater than unmodified
paper products
2

3. Materials Used in this Project
• Pulp
• Brazil
• BCTMP
• CNF
• Hardwood
• Softwood
• Starch Nanoparticles
• Ecosphere 2777
3

4. Pulp and Paper Industry
• Origin of papermaking dates back to
~100 AD China
• Rags, hemp and grass were beat against
stone mortars to break down its fibres
• Pulping wood was developed ~1800s
• More abundant fibre source
• Still used in modern pulp & paper
manufacturing
• In modern times, papermaking is a
large integration operation including:
• Foresting
• Lumbermilling
• Pulp & Paper Manufacturing
• Conversion
4
Teschke K. (2011). Paper and Pulp Industry: General Profile. Encyclopedia or Occupational Health and Safety. Chapter 72.
Retrieved from http://www.iloencyclopaedia.org/part-x-96841/paper-and-pulp-industry

5. Pulp
• Main component is cellulose
• Strong H-bonds that holds the fibres
together
• 600 to 1500 repeating alternating D-
glucose molecules
• Modified using additives
• Different types of woods have
different proportions of components
• Our project involves Softwoods and
Hardwoods pulp
5
Keefe A. & Teschke K. (2011). Paper and Pulp Industry: Fibre Sources for Pulp and Paper. Encyclopedia or Occupational
Health and Safety. Chapter 72. Retrieved from http://www.iloencyclopaedia.org/part-x-96841/paper-and-pulp-industry
Royal Society of Chemistry (2013). Paper Conservation Cellulose Acid Hydrolysis. Education in Chemistry Magazine.
Retrieved from: http://www.rsc.org/education/eic/issues/2013March/paper-conservation-cellulose-acid-hydrolysis.asp
Table 1. Chemical Compositions of Pulp and its Sources (Keefe & Teschke (2011)

6. Pulping
• Process of exposing fibrous
structures of pulp by rupturing
bonds within wood structure
• Mechanical
• Chemical
• Pulping process was already
done and pulp was provided by:
• Suzano Papel e Celulose (Brazil)
• West Fraser (BCTMP)
6
Anderson J., Anastrakianakis G. & Keefe A. (2011). Paper and Pulp Industry: Pulping. Encyclopedia or Occupational
Health and Safety. Chapter 72. Retrieved from http://www.iloencyclopaedia.org/part-x-96841/paper-and-pulp-industry

7. Properties of Pulp
Brazil
7
• 0.0176 mM/g of COOH content
• Hardwood from Eucalyptus trees
• Shorter fiber length, lower pulp
strength
BCTMP
• 0.024 mM/g of COOH content
• Zeta potential: -25.3 mV
• Softwood
• Longer fiber length

8. Bleached Chemical Thermo-Mechanical Pulp
(BCTMP)
• Softwood
• Used to manufacture coated boards,
printing/writing paper and paper
towel/napkin grades
• From Lodgepole Pine and White Spruce
trees
• Advantages
• Produce 2x the yield of pulp compared to
other chemical pulps (85% vs. 42%)
• More environmentally friendly →
chlorine-free bleaching
8
CANNELL, E. (2000, May 1). PULP & PAPER MAGAZINE:The Future of BCTMP. Retrieved from
http://legacy.risiinfo.com/magazines/May/2000/PP/pulp-paper/magazine/may/2000/The-Future-of-BCTMP.html
Softwood BCTMP provided by West Fraser

9. Optical Microscopy Images of BCTMP
• Long fibers that are a couple of mm in length
• Small amount of fibrillated fibers
9

10. What is CNF?
• Referred to as Cellulose Nanofibers (CNF) or Microfibrillated Cellulose (MFC)
• Size: 20-50 nm
• Nanocomponent of cellulose, acquired by mechanical methods (shearing)
using high pressure homogenizer
• Contains amorphous and crystalline regions
• Our project involved 2 different types of CNF samples:
• CNF from Hardwood (CNF-H)
• CNF from Softwood (CNF-S)
10 Nasirpour A., Fathi M. & Rezzei A. (2015). Application of Cellulosic Nanofibers in Food Science Using
Electrospinning and Its Potential Risk. Comprehensive Review in Food Science and Food Safety. Vol 14-3.
Retrieved from: http://onlinelibrary.wiley.com/doi/10.1111/1541-4337.12128/pdf

11. Properties of CNF
• Lightweight material
• Renewable resource and biodegradable
• High surface area and high tensile strength (138 GPa)
compared to pulp fiber (2 GPa)
• Hydroxyl groups on the surface allow for various chemical
modifications
• Negatively charged
11
CNC
5-20 nm
Mircofibrillated
Cellulose (CNF/MFC)
20-50 nm
Elementary fibrils
5 nm
Chemical structure
Amorphous regionCrystalline region
Pulp Fibers

12. CNF-Hardwood
• 0.048 mM/g of COOH content
• Zeta Potential: -36.1 mV
12
CNF-H

13. CNF-Softwood
• 0.064 Mm/g of COOH content
• Zeta Potential: -22.5 mV
13
CNF-S

14. Optical Microscopy Images of CNF-H
• Few long fibers that are mm in length
• Most fibers are hundred microns in length
14

15. Optical Microscopy Images of CNF-S
• Some long fibers that are mm in length
• Considerable amount of fibrillated fibers that are hundred microns in length
15

16. Starch Nanospheres
• Starch
• natural, renewable, and biodegradable polymer
• consists of linear amylose (~75%) and branched
amylopectin (~25%)
• contains both amorphous and crystalline regions
16
Corre, D. L., Bras, J., & Dufresne, A. (2010). Starch Nanoparticles: A
Review. Biomacromolecules, 11(5), 1139-1153. doi:10.1021/bm901428y

17. Ecosphere 2777
• Starch particles cationically modified by
quaternary amine
• Zeta potential: 16.9 mV
• Size measured by DLS: Rh = 92.5 nm
17
Ecosphere 2777

18. Traditionally Used Wet Strength Agents
• Urea-Formaldehyde (UF) resin
• network created by self-crosslinking
• not environmental friendly
• Polyamide Epichlorohydrin (PAE)
• formation of covalent bonds between PAE and cellulose
fibers
• negatively impacts environment due to organic chloride →
limited use in paper mills now
18
Espy, H. H. (1995). The mechanism of wet-strength development in paper:
a review. Tappi Journal, 78(4), 90-100.

19. Advantages of CNF and Cationic Ecosphere
• High surface area of CNF and Ecospheres → increases the
number of bonds between the pulp fibers
• CNF can be modified to have positive charges on the surface
• Negatively charged pulp will have electrostatic interaction
with cationic Ecospheres and modified CNF
19

20. Forming Handsheets for Physical Testing
• TAPPI T-205 “Forming Handsheets for Physical Tests
of Pulp”
• Disintegration (mixing and dispersion of pulp fibres)
• Sheetmaking (filtration of pulp)
• Couching (Blotting and rolling of fresh sheet)
• Pressing
• Drying
• Testing of sheets (Tensile strength)
• Followed this stepwise procedure, making appropriate
alterations
• Included procedure in adding additives to pulp
20

21. Disintegration
• Process of breaking and dispersing pulp fibres into
smaller components
• Guidelines from Pulp Company:
• Dilute to 4-8 wt% (we used 4%), mix for minimum of 20
minutes
• Even after several hours, still chunky consistency
• Sheets were not homogenous
• Guidelines from TAPPI T 205:
• Dilute to 1.2 wt% (we used 1.5%), mix at high rpm
• Dilute to 0.3 wt%, stir at high rpm until properly mixed
• Starting at a lower consistency produced more
homogenous sheets
• Final procedure: Mix at 1.5 wt% for 1 hour, dilute to
0.3 wt% and mix for 30 mins
21
Disintegration of pulp

22. Sheetmaking
• Glass Filtration
• screening trial of sheetmaking
• Pros:
• Setup was stable  allowed for more
homogenous filtration
• Cons:
• Sheets were too small  could not be
properly tested
22 Glass filtration setup

23. Sheetmaking
• Buchner Funnel
• Pros: Larger diameter, allows for
larger sheets
• Cons: Membrane was not completely
flat, resulted in non-homogenous
areas
• Different types of filter
membrane used  led to sheet
sticking to it
• Cloth + metal mesh membrane
was made to avoid sticking
23
Buchner funnel setup
Cloth + metal mesh

24. Sheetmaking
• Filtration
• Set-up designed and made by
Dr. Yao
• Wire mesh (size: 200 mesh)
used instead of cloth or filter
paper to eliminate problem
with sheet sticking
• Solution diluted by adding
additional 1250 mL of water,
mixed and allowed to settle
before applying vacuum
• More homogenous sheets
24
Current filtration set-up
Wire mesh

25. Couching/Pressing
• Filter papers were used as blotters,
rolled to soak up excess water on
sheets
• Preliminary pressing step
• More homogenous sheets, prevented
wrinkling and greater tensile strength
• Implemented a standard pressing
procedure
• Hydraulic press at 50 psi for 5 mins, then
again for 2 mins after replacing blotters
25
Hydraulic press

26. Modifying Pulp
• Created modified pulp solution by
mixing pulp and additive
• Initial attempt:
• Combined 0.3 wt% pulp and 0.3 wt%
additive together and mixed for 10
mins
• Sheets were not homogenous due to
formation of aggregates
• Decreased additive from 0.3 wt%
to 0.1 wt%, added dropwise and
mixed for 30 mins
• Allowed for better dispersion of
additive within pulp solution
• More homogenous sheets26
Additive
Modified Pulp Solution

27. Drying
• Hotplate method
• Sheet was placed between
glass plates and heated on
hotplate at 90oC with weight
placed on top for 5 min,
then air dried
• Heat was not distributed
evenly onto sheet, bottom
was heated but top was not
• Very inefficient when drying
multiple sheets
27 Hotplate method of drying

28. Drying
• Current method
• Multiple handsheets are placed between glass
plates and dried overnight in oven at 70o C
• Weights placed on top of plates to prevent
wrinkling
28
Oven drying method

29. Testing
• Tensile Strength (TS): Maximum applied tensile force a
specimen can withstand before rupturing
• Force (NZ) per unit width (m), NZ/m
• Force is applied through the z-axis by UMT machine, width
of strip is 0.015m
• Factors affecting: fibre strength, fibre length and bonding
• TS = FZ/(width of strip)
• Tensile Index (TI): Relates the strength of the
specimen with the amount being loaded
• Provides relative strength of sheet
• Tensile strength (NZ/m) divided by grammage (g/m2)
• TI = TS/(mass of strip/Area of strip)
29
Muchorski D. (2006). Tensile properties of paper and paperboard. TAPPI (2), T 494. Retrieved
from: http://www.tappi.org/content/sarg/t494.pdf

30. Testing
• 5 15mm x 60mm strips are cut and
weighed from each handsheet and
tested
• Universal Testing Machine is used to
apply a stretching force to the z-axis
• Machine usage provided by Dr. Boxin Zhao
• 5 dry tests and 5 wet tests
• Wet test: 30 µL is dropped onto middle of strip
prior to test
• Water affects tensile strength by affecting the
swelling behaviour of fibres
30
Strips cut from handsheet
Testing using UTM

31. Testing
• Tensile strength of different types of
sheets are compared to a 100% pulp
sheet  control group
• Literature value of raw pulp is given in
table
• Preliminary testing of pulp done with a
100% BCTMP sample
• Dry tensile index of 25.97 Nm/g
• Confirms that data is agreeable and
reproducible
31 Hsieh J. & Yoo S. (2010). Enzyme-Assisted Preparation of Fibrillated Cellulose Fibers and Its Effect
on Physical and Mechanical Properties of Paper Sheet Composites. Ind Eng Chem Res. Vol 49 Issue
5. Retrieved from: http://pubs.acs.org/doi/abs/10.1021/ie901621n

32. Current Additives to Pulp
• CNF-GTMAC
• CNF-g-pAPTAC and CNF + pAPTAC
• Ecosphere 2777
32

33. CNF-GTMAC
• CNF is modified with cationic
Glycidyltrimethylammonium chloride (GTMAC)
• Carried out in an aqueous solution instead of
using an organic solvent such as DMSO
• safer, easier to scale up for a large scale process
33

34. CNF-GTMAC
• Procedure: Dissolved CNF in NaOH solution and stirred
the mixture at 50°C for 4 hours, dropwise added
GTMAC over 1 hour and stirred the mixture at 60°C
• Zeta potential: 39.7 mV, higher than CNF (-26.1 mV).
• Positively charged so it will better adhere to negatively
charged pulp
• After 1 week of storage, CNF-GTMAC is more stable
than CNF
34
CNF-GTMAC (left) and unmodified CNF (right)

35. Preliminary Tensile Index Results using CNF-
GTMAC
• at both 5% and 10%, the addition of CNF-
GTMAC to pulp increased the dry and wet
tensile index over 20%
35
Samples
Tensile index Nm/g % increase
Dry Wet Dry Wet
100% pulp 21.16 2.12
CNF-GTMAC
5% 36.87 2.72 54.20 28.30
10% 38.04 3.09 79.80 45.80

36. Polymerization of (3-
acrylamidopropyl)triethylammonium (APTAC)
• Free radical polymerization using ammonium
persulfate (APS) as initiator
• Procedure: Mixed CNF with initiator APS and
bubbled the mixture with N2 gas for 1 hr, added
APTAC in dropwise fashion, then stirred the
mixture at 70°C overnight.36
CNF
APTAC

37. pAPTAC
• In 125 mg of CNF-g-pAPTAC, 0.8 wt%
is the polymer
• 0.038 mM/g
• Zeta potential:
• CNF-g-pAPTAC (grafted): –20.8 mV
• CNF-pAPTAC (mixed) (1:0.01): –20.8 mV
• no difference in zeta potential when pAPTAC
is grafted or mixed with CNF
37

38. Preliminary Tensile Index Results using
pAPTAC
• only the samples with 10% CNF-g-pAPTAC
added to the pulp showed a 20% increase for
both the dry and wet tensile index38
Samples
Tensile index
Nm/g
% increase
Dry Wet Dry Wet
100% pulp 21.16 2.12
CNF-g-
pAPTAC
5% 35.58 2.13 49.80 0.50
10% 43.55 2.89 105.80 36.30
CNF:pAPTAC
(1:0.5)
5% 23.63 1.52 6.70 -28.30
10% 29.85 2.27 41.10 7.10

39. Ecosphere 2777
• both 5% and 10% Ecosphere 2777 added to the pulp showed much
greater than 20% increase for both the dry and wet tensile index
39
Samples
Tensile index
Nm/g
% increase
Dry Wet Dry Wet
100% pulp 21.16 2.12
Ecosphere
2777
5% 41.23 3.74 94.80 76.40
10% 38.06 5.15 79.90 142.90

40. Ecosphere 2777:CNF-S
• zeta potential of the mixture of Ecosphere 2777 and CNF-S increased when
increasing the amount of 2777
• zeta potential stayed almost unchanged after the ratio exceeded 0.140
Eco2777:CNF-S
Zeta potential
(mV)
0 -22.5
0.1 15.2
0.25 14.9
0.5 16.0
1 16.7
2 16.9
3 20.2
5 16.6

41. TEM Image of Ecosphere 2777:CNF-S (1:1)
• dark coloured circles
embedded on fibers
show that ecosphere
particles have bonded
to CNF-S
41

42. Tensile Index Results of Ecosphere 2777:CNF-
S (1:1)
• when more than 3% of Ecosphere 2777 mixed with
CNF-S at 1:1 ratio is added to the pulp, the dry and
wet tensile index increased by more than 20%
• however, standard deviation is high, more
homogenous sheets need to be made42
Samples
Tensile index
Nm/g
% increase
SD
Dry Wet Dry Wet Dry Wet
100% pulp 25.17 2.81 1.87 0.56
Ecosphere
2777:CNF-S
(1:1)
1% 30.18 3.20 19.93 13.97 5.14 0.97
3% 34.05 3.39 35.30 20.62 2.28 1.24
5% 43.16 4.03 71.49 43.44 6.06 1.22
8% 41.26 3.87 63.96 37.82 5.13 0.56

43. Tensile Index Results of Ecosphere 2777:CNF-
S (1:2)
• when more than 1% of Ecosphere 2777 mixed with CNF-S at 1:2
ratio is added to the pulp, the dry and wet tensile index
increased more than 20%
• however, the trend is not consistent, perhaps due to formation of
large aggregates43
Samples
Tensile index
Nm/g
% increase
SD
Dry Wet Dry Wet Dry Wet
100% pulp 24.20 2.29 1.22 0.26
Ecosphere
2777:CNF-S
(1:2)
1% 29.34 2.82 21.24 23.38 5.61 0.52
3% 32.53 2.84 34.43 24.25 6.95 1.17
5% 51.21 3.42 111.60 49.50 7.38 0.73
8% 39.81 3.14 64.50 37.47 12.83 0.24

44. Ecosphere 2777:CNF-H
• zeta potential of the mixture of Ecosphere 2777 and CNF-H increased when
increasing the amount of 2777
• zeta potential stayed almost unchanged after the ratio exceeded 144
Eco2777:
CNF-H
Zeta potential
(mV)
0 -36.1
0.1 10.1
0.25 10.5
0.5 12.4
1 16.7
2 19.1
3 18.8
5 19.4

45. TEM Image of Ecosphere 2777:CNF-H (1:1)
• dark coloured circles
embedded on fibers
show that Ecosphere
particles have
bonded to CNF-H
45

46. Tensile Index Results of Ecosphere 2777:CNF-
H (1:1)
• when more than 1% of Ecosphere 2777 mixed with CNF-H at 1:1
ratio is added to the pulp, the dry and wet tensile index
increased more than 20%
• however, standard deviation is high, more homogenous sheets
need to be made46
Samples
Tensile index
Nm/g
% increase
SD
Dry Wet Dry Wet Dry Wet
100% pulp 25.17 2.81 1.87 0.56
Ecosphere
2777:CNF-H
(1:1)
1% 30.50 3.50 21.17 24.66 3.42 0.30
3% 41.36 4.14 64.34 47.19 5.69 0.53
5% 37.59 4.34 49.36 54.40 3.37 0.49
8% 39.62 4.48 57.42 59.55 3.70 0.84

47. Tensile Index Results of Ecosphere 2777:CNF-
H (1:2)
• when more than 3% of Ecosphere 2777 mixed with CNF-H at 1:2
ratio is added to the pulp, the dry and wet tensile index
increased more than 20%
• trend is consistent, however standard deviation is high, more
homogenous sheets need to be made
47
Samples
Tensile index
Nm/g
% increase
SD
Dry Wet Dry Wet Dry Wet
100% pulp 24.20 2.29 1.22 0.26
Ecosphere
2777:CNF-H
(1:2)
1% 25.15 2.70 3.92 18.09 2.86 0.37
3% 34.42 2.79 42.22 22.00 6.87 0.79
5% 38.59 2.96 59.47 29.46 4.24 0.31
8% 41.34 4.24 70.84 85.44 13.15 0.43

48. Comparison of Ecosphere 2777:CNF (1:1 and
1:2)
• Comparing the % increase in tensile index of Ecosphere 2777:CNF
at ratios of 1:1 and 1:2, adding more CNF did not increase the
tensile index very much and in some cases had an even lower
tensile index48
Samples
% increase
Samples
% increase
Dry Wet Dry Wet
Ecosphere
2777:CNF-S
(1:1)
1% 19.93 13.97
Ecosphere
2777:CNF-S
(1:2)
1% 21.24 23.38
3% 35.30 20.62 3% 34.43 24.25
5% 71.49 43.44 5% 111.60 49.50
8% 63.96 37.82 8% 64.50 37.47
Ecosphere
2777:CNF-H
(1:1)
1% 21.17 24.66
Ecosphere
2777:CNF-H
(1:2)
1% 3.92 18.09
3% 64.34 47.19 3% 42.22 22.00
5% 49.36 54.40 5% 59.47 29.46
8% 57.42 59.55 8% 70.84 85.44

49. Ecosphere 2777:CNC
• zeta potential of the mixture of Ecosphere 2777 and CNC increased when
increasing the amount of 2777
• zeta potential stayed almost unchanged after the ratio exceeded 249
Eco2777:CNC
Zeta
potential
(mV)
0 -41.45
0.1 -20.4
0.25 -18.3
0.5 -13.3
1 12.55
2 15.45
3 16.85
5 15.85

50. TEM Image of Ecosphere 2777:CNC (1:2)
• dark coloured circles are
Ecosphere particles, light
coloured rods are CNC
• appears that Ecosphere
particles mixed well with
CNC
50

51. Tensile Index Results of Ecosphere 2777:CNC
(2:1)
• only the samples with 8% Ecosphere 2777:CNC at 2:1 ratio added to the pulp
showed a 20% increase for both the dry and wet tensile index
• wet tensile index even decreased due to CNC’s ability to disperse well in water 
when the paper absorbed water, CNC lost it’s adhesion capability
51
Samples
Tensile index
Nm/g
% increase SD
Dry Wet Dry Wet Dry Wet
100% pulp 20.37 3.06 1.63 0.07
Ecosphere
2777:CNC
(2:1)
1% 23.96 2.65 17.62% -13.59% 4.68 0.28
3% 24.07 3.01 18.16% -1.74% 4.38 0.49
5% 38.1 2.93 87.04% -4.35% 7.38 0.79
8% 30.95 3.95 51.94% 29.01% 1.24 0.34

52. Conclusion
• From the results gathered so far
• Ecosphere 2777 mixed with CNF-H and CNF-S and
added to pulp reach the goal of increasing the dry
and wet tensile index by 20%
• CNF-GTMAC added to pulp also shows promising
preliminary results and can further be tested as
necessary
• CNC will not be used again since results did not
reach goal and also more expensive compared to
CNF
52

53. Conclusion
• Next steps
• Handsheet making process can be further
improved in order to make more homogenous
sheets to decrease standard deviation and produce
more reliable results
• Make and test sheets:
• Ecosphere 2777:CNF-H/S at 2:1 ratio
• CNF-H and CNF-S
• Ecosphere 2777 mixed with CNF-S dry product provided
by company
53

54. 54
THANKS FOR LISTENING
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