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Development and characterization of compatible cellulose blend membranes using cellulose and other natural biopolymers using a novel solvent system. By Eugene F. Douglass, MS, PhD Department of Chemistry Nazarbayev University, Astana, Kazakhstan & Richard Kotek, PhD

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By eugene f douglass ms phd department of chemistry nazarbayev university astana kazakhstan

Development and characterization of compatible cellulose blend membranes using cellulose and other natural biopolymers using a novel solvent system

By

Eugene F. Douglass, MS, PhD

Department of Chemistry

Nazarbayev University, Astana, Kazakhstan

&

Richard Kotek, PhD

TECS, College of Textiles

North Carolina State University, Raleigh, NC USA

June 28, 2010

1


Objectives

Objectives -

Reviewing briefly the literature, and previous work with this system. To summarize the recent work developing new fibers and membranes using our novel solvent system.

To show the development of biopolymer blend cellulose membranes, using previous work as a foundation.

To show the characterization of the membranes.

To extend the preliminary goals of the research into a new creative area, developing brand new materials that may have use in the membrane industry, and to characterize these new materials.

2


1 introduction

1 - Introduction

5


By eugene f douglass ms phd department of chemistry nazarbayev university astana kazakhstan

  • Layer of material which serves as a selective barrier

  • Barrier is between two or more phases

  • Remains impermeable to specific particles, molecules or substances

  • Osmotic forces enable free flow of solvents

  • Some components are allowed passage into permeate stream

  • Others are retained and remain in the retentate stream

6


Cellulosic sources

Cellulosic sources

Cellulose most abundant naturally occurring polymeric raw material – very cheap raw material

Wood pulp, cotton, other plant fibers, or plant waste

Figure 1- Molecular structure of cellulose.11

7


Examples

Examples

Cellulosic fibers and membranes

Natural cellulose fibers: cotton, linen, & flax

Regenerated cellulose: rayon fiber and film, cellophane film

Cellulose dissolved in a solvent: Lyocell fiber and film

Cellulose derivatives: nitrocellulose, celluloid, cellulose acetate fibers and films

Early solution methods – Regenerated cellulose: Cellulose xanthate is made, dissolved, then regenerate the cellulose chemically.

Viscose process

  • Rayon

  • Problems: dangerous solvent, toxicity of waste material

    Recent solution methods – Dissolve cellulose in a solvent system

    Lyocell process – prime commercial process

  • Lyocell

  • Problems: solvent instability issues, expensive

8


Amine and counter ion dissolution

Amine and counter ion dissolution

  • ac sin γ projection;

  • ab projection2

Zn+2 > Li+ > Ca+2 > Mg+2 > Ba+2 > Na+ > NH4+ > K+

SCN- > I- > PO4-3 > Br- > Cl- > NO3- > SO4-2 > ClO3-

Order of decreasing swelling of cellulose2

Figure 2 – Swollen cellulose – crystal structure

9


Amine and metal salt association

Amine and metal salt association

Ionic interactions assisting dissolution

Figure 3 – Coordination of ED and KSCN in solution9 Frey

10


2 development of cellulose blend membranes

2 - Development of cellulose blend membranes

11


Previous work at north carolina state university

Previous work at North Carolina State University

Hyun Lee12– developed cellulose fibers from this optimized solvent blend, and did some basic membrane investigation

Possible porous membrane

Severe yellowing upon aging

Problems:

  • could not reproduce this structure using means described

  • Used non-reproducible method of casting

    • Used tape layers on glass rods

    • Draw down on glass plate, hard to remove

Figure 4 – Porous cellulose membrane12

12


Development of new casting process for reproducibility

Development of new casting process for reproducibility

Reproducibility is required

  • Casting table

  • Uniform casting bar

  • Cast on PET plastic film for ease of placing in coagulation bath and removal of coagulated membranes

    Obtained casting table and bars from Byk-Gardner

    Obtained casting PET film and drawdown panels for sample membranes

13


Objective dissolution of cellulose and other biopolymers dp 450

Objective: Dissolution of cellulose and other biopolymers (DP 450)

  • Simple setup for dissolution, paddle stirrer apparatus

Figure 5 - 7% free flowing ED/KSCN cellulose (DP = 450) solution

Figure 6 – Dissolution apparatus

14


By eugene f douglass ms phd department of chemistry nazarbayev university astana kazakhstan

Microscopic views of dissolution

Table 1 - Different swelling and dissolution mechanisms for cotton and wood fibers in NMMO – water mixtures at various water contents.3

15


Background of invention of new material

Background of invention of new material

Cellulose and starch are polysaccharides

Bond linkage of glucose units different

Solvent for cellulose works, perhaps would work for starch.

Discussion with Drs. Kotek, Venditti, and Pawlak: Can starch make a membrane with this solvent system? No, could we do a blend??

Motivation

Attempt blend with starch for membranes; success!

Based on success with starch; chitosan, chitin and soy protein were also tried.

Both porous and nonporous membranes were obtained, this section describes the development of cellulose blended with starch to form a useful membrane.

34


Table 2 types of starches used all are blends

Table 2 -Types of starches used – all are blends

Figure 7 - Amylose

Figure 8 - Amylopectin

35


3 characterization of porous cellulose blend membranes with starch

3 - Characterization of porous cellulose blend membranes with Starch

36


Sem characterization of blend membranes cellulose and corn starch

SEM characterization of blend membranescellulose and corn starch

Cross sections of 50/50 cellulose and corn starch blend membranes

Figure 9– 500x cellulose / corn starch blend membrane

Figure 10 – 5000x cellulose / corn starch blend membrane

37


Cross sections of 50 50 cellulose and high amylose starch blend membranes

Cross-sections of 50/50 cellulose and high amylose starch blend membranes

Cellulose and high amylose starch

Incompatible

Figure 11 – 500x cellulose / high amylose starch blend membrane

Figure 12– 5000x cellulose / high amylose starch blend membrane

38


Cellulose and waxy maize starch

Cellulose and waxy maize starch

Cross-sections of 50/50 cellulose and waxy maize starch blend membranes

1000 nm pore size

Figure 13– 500x cellulose / waxy maize starch blend membrane

Figure 14– 5000x cellulose / waxy maize starch blend membrane

Compatible!

39


Tga analysis of cellulose membrane and 50 50 cellulose waxy maize starch membrane

TGA analysis of cellulose membrane and 50/50 cellulose / waxy maize starch membrane

100

100

Mass %

30

30

20o C

710o C

Figure 15- Cellulose membrane: onset 332º C, end 371º C, ash level about 28%

20o C

710o C

Figure 16: Cellulose / wm starch blend membrane: onset 272º C, end 324º C, ash level about 20%

41


Wide angle x ray scattering of blend membranes

Wide Angle X-ray Scattering of blend membranes

Cellulose II structure Amorphous structure

Peaks at 16,17 and 23 2θ Broad peak at 20-22 2θ

Cellulose / Waxy Maize Starch membrane

Figure 18– cellulose / waxy maize starch membrane

Figure 17– cellulose membrane

42


By eugene f douglass ms phd department of chemistry nazarbayev university astana kazakhstan

Table 3 - Tensile property comparison of cellulose and cellulose blend membranes

43


4 cellulose and proteins blended in solution to make membranes

4 - Cellulose and proteins blended in solution to make membranes

47


Development of cellulose soy protein blend membranes

Development of cellulose / soy protein blend membranes

Based on success with Starches, we thought protein might work

First attempt with Brim Soy Protein isolate, received from USDA labs on NCSU campus

  • Two protein types in the Brim blend

  • Dissolves well in solvent blend

    ADM soy materials received from NC Soy Council

  • SAF soy protein

  • Archon F soy protein concentrate

  • Profam 974 soy protein isolate (comparable to Brim)

48


By eugene f douglass ms phd department of chemistry nazarbayev university astana kazakhstan

Sample blend membranes made from each protein, to determine best quality membranes.

  • Brim and Profam 974 made best quality membranes

  • These were used for main characterization

    Determine ideal mass ratios of Soy protein to cellulose using Profam 974 at 40, 30 and 20% by characterization of each mass percent membrane.

49


5 characterization of cellulose soy protein blend membranes

5 – Characterization of cellulose / soy protein blend membranes

50


Sem cross section micrographs of 50 50 cellulose soy protein blends compatible

SEM cross section micrographs of 50/50 cellulose – soy protein blends – Compatible!

Figure 20 – 50/50 Cellulose/Profam 974

membrane, 5000x

Figure 19– 50/50 Cellulose/brim membrane, 5000x

51


Tga analysis cellulose membrane compared to cellulose brim soy protein blend

TGA Analysis - cellulose membrane compared to cellulose/brim soy protein blend

100

100

Mass %

Figure 21 - Cellulose membrane: Onset 332º C, end 371º C, ash about 28%

30

30

20o C

710o C

Figure 22- Cellulose / brim blend membrane: Onset 241º C, end 342º C, ash about 28%

20o C

710o C

52


Tga analysis cellulose membrane compared to cellulose profam 974 soy protein blend

TGA Analysis - cellulose membrane compared to cellulose/Profam 974 soy protein blend

100

100

Mass %

30

30

Figure 23- Cellulose membrane: Onset 332º C, end 371º C, ash level about 28%

20o C

710o C

Figure 24- Cellulose / Profam 974 blend membrane: Onset 284º C, end 344º C, ash level about 9%

20o C

710o C

53


Table 4 summary of tga results for soy protein cellulose blend membranes

Table 4 - Summary of TGA results for soy protein / cellulose blend membranes

Table 8 - Comparison of TGA results between membranes

54


Wide angle x ray scattering of profam 974 blend membrane

Wide Angle X-ray Scattering of Profam 974 blend membrane

Cellulose II Structure Amorphous Structure

Peaks at 16,17 and 23 2θ Broad Peak at 20-22 2θ

Figure 25– Cellulose membrane

Figure 26– Cellulose / Profam 974 membrane

55


Wide angle x ray scattering of stretched soy protein blend membranes

Wide Angle X-ray Scattering of Stretched Soy Protein blend membranes

Amorphous Structure Amorphous Structure

Peaks at around 14 and 21 2θ Around 14 and 21 2θ

Notice

Notice

Figure 27– Cellulose / Brim blend

Figure 28– Cellulose / Profam 974 blend

56


Tensile properties summary

Tensile Properties Summary

Table 5 – Comparison of Tensile properties for soy blend membranes

57


6 later work at ncsu

6 – Later work at NCSU

59


By eugene f douglass ms phd department of chemistry nazarbayev university astana kazakhstan

Made blend fibers from cellulose / waxy maize, and cellulose / soy protein blends.

Cross-linked cellulose and cellulose blend membranes to prevent falling apart in long term water contact.

60


7 coming work at nazarbayev university brief discussion

7 – Coming work at Nazarbayev UniversityBrief Discussion

61


Conclusions

Conclusions

New dissolution process development:

Using a special solvent system of ED/KSCN in a 65/35 mass % ratio, functional porous and non-porous membranes were produced that have comparable physical properties to other methods of making cellulose membranes.

New material development:

Using the same solvent system, starch was blended with cellulose in the solution and cast to make functional porous blend membranes, that are stronger than the cellulose porous membranes developed earlier, and very water absorbent.

62


Conclusions1

Conclusions

Using the same solvent system, soy protein was blended with cellulose to make functional non-porous blend membranes, that are strong and even more water absorbent than the blend membrane with starch.

The casting and drying processes were optimized to deal with issues of shrinkage that causes wrinkling and variable film thicknesses

Other polysaccharides (chitosan and chitin), and protein (keratin from hair) were also used to make functional blend membranes with cellulose, suggesting further applications for this system.

63


8 references

8 - References

64


By eugene f douglass ms phd department of chemistry nazarbayev university astana kazakhstan

Ott . Cellulose and cellulose derivatives : Molecular characterization and its application. Burlington: Elsevier; 1954.

Khare VP, Greenberg AR, Kelley SS, Pilath H, Roh IJ, Tyber J. Synthesis and characterization of dense and porous cellulose films. J ApplPolymSci 2007;105(3):1228-36.

Cuissinat C, Navard P. Swelling and dissolution of cellulose part 1: Free floating cotton and wood fibres in N-methylmorpholine-N-oxide-water mixtures. Macromolecular Symposia 2006;244(1):1.

Cuissinat C, Navard P. Swelling and dissolution of cellulose part II: Free floating cotton and wood fibres in NaOH-water-additives systems. Macromolecular Symposia 2006;244(1):19.

Fink H, Weigel P, Purz HJ, Ganster J. Structure formation of regenerated cellulose materials from NMMO-solutions. Progress in Polymer Science 2001 11;26(9):1473-524.

Swatloski RP, Spear SK, Holbrey JD, Rogers RD. Dissolution of cellulose with ionic liquids. J Am ChemSoc 2002;124(18):4974-5.

Zhang . 1-allyl-3-methylimidazolium chloride room temperature ionic liquid: A new and powerful non-derivatizing solvent for cellulose. Macromolecules 2005;38(20):8272.

Hafez MM, Pauls HW, inventors. Method for preparing thin regenerated cellulose membranes of high flux and selectivity for organic liquids separations. Exxon Research and Engineering Co., editor. 4496456. 1985 1/29/1985

Frey M, Li L, Xiao M, Gould T. Dissolution of cellulose in ethylene diamine/salt solvent systems. Cellulose 2006 04/29;13(2):147-55.

Cao Y. Preparation and properties of microporous cellulose membranes from novel cellulose/aqueous sodium hydroxide solutions. Journal of Applied Polymer Science [Internet]. [revised 2006;102(1):920.

Metzger J. Carbohydrate structures http://chemistry.gcsu.edu/~metzker/Common/Structures/Carbohydrates/

Lee HJ. Novel cellulose solvent system and dry jet wet spinning of Cellulose/ED/KSCN solutions. Raleigh, NC: North Carolina State University; 2007. Available from: unrestricted

65


9 acknowledgements

9- Acknowledgements

North Carolina State University, College of Textiles including

  • Drs. Richard Kotek, Peter Hauser and Alan Tonelli

  • Dr. Richard Venditti and Dr. Joel Pawlak, College of Natural Resources

  • Chuck Mooney, Birgit Anderson and Theresa White

    Nazarbayev University, Astana, Kazakhstan seed funding to disseminate this work, and develop further work

  • Drs. Kenneth Alibek SST, Sergey Mikhalovsky College of Engineering

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