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Plasma polymers for controlled surface chemistries PPT

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Plasma polymers as surfaces of
controllable chemistry
Morgan Alexander
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Environment
Organic film
Surface
Components of a coating
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Cold/non-equilibrium low pressure
plasma apparatus
VACUUM TIGHT VESSEL
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ENERGY SOURCE Capacitively or
inductively coupled, to sustain the
plasma after the initial ionisation event.
w=0 Hz(DC)-13.56 kHz(RF)- 2.45 GHz
(MW).
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PUMPING
Used to regulate the
pressure in the reactor. Typically,
base pressure 1 Pa (10-2 torr)
monomer pressure 40 Pa
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GAS INTRODUCTION SYSTEM
Used to regulate the
introduction of monomer vapour and
gases.
PLASMA
PLASMA DEPOSIT
SUBSTRATE
(Situated within, or downstream of the plasma)
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Kelly, J. M., Short, R. D. & Alexander, M. R. Experimental evidence of a relationship between monomer plasma residence time and carboxyl group retention in acrylic acid
plasma polymers. Polymer 44, 3173-3176 (2003).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Exploration of plasma polymerised acrylic acid (ppAAc)
coatings to promote adhesion to aluminium: rationale
Environmental drive to remove chromates from processes.
H2C=CH
C
HO
O
OH
C
O
O
+
CH2 CH ~
O
C
O
CH2 CH ~
OH
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
C o u n ts x 1 0
Molecular structure of ppAAc: Static SIMS
4
C o u n ts x 1 0
14
P=2W
O-
12
10
OH
x 35
3.0
99
4
x 50
P=20W
99
113
8
113
125
1.5
145
6
-
4
CH
143
C H
2 41
-
145
2
59
0
125
71
73
73
m /z
50
59
41
100
150
0
50
m /z
100
150
m/z 71, 143, 215 and 287
H[CH2-CH(COOH)]n-CH=CH-C(=O)O-, where n=0 to 3.
C o u n ts
250
157
171
(cyclic structures are also possible)
215
200
150
m/z=361 H[CH2-CH(COOH)]4-CH2-CH2-C(=O)O189
229
100
243 261
289
287
301 315
361
387
50
150
200
300
250
m /z
350
m/z=387 CH2=CH-[CH2-CH(COOH)]4-CH2-CH2-C(=O)O-
400
i.e. 6 monomer repeat units
Alexander, M. R. & Duc, T. M. The chemistry of deposits formed from acrylic acid plasmas. J. Mater. Chem. 8, 937-943 (1998).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
C1s core level from ppAAc
P = 2 W
C-OX
C-C/CH
C(=O)-OX
P = 20 W
C-C(=O)-OX
C=O
Alexander, M. R. & Duc, T. M. The chemistry of deposits formed from acrylic acid plasmas. J. Mater. Chem. 8, 937-943 (1998).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
C1s core level from TFE derivatised PAA
(CH2 CH)n
C
O O-CH2CF3
Alexander, M. R. & Duc, T. M. The chemistry of deposits formed from acrylic acid plasmas. J. Mater. Chem. 8, 937-943 (1998).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Full quantification of the functional and elemental
composition
[O ]/ [C ]
C (= O )O H
C (= O )O -C
C (= O )O -C
C -O H
C -O -C
C=O
C H 2 /C -C
2W
0.72
20 W
0.39
22
5
5
0
0
1
66
4
11
11
0
0
3
74
Alexander, M. R. & Duc, T. M. The chemistry of deposits formed from acrylic acid plasmas. J. Mater. Chem. 8, 937-943 (1998).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Carboxylic acid concentration as a function of
copolymer in feed
CH2=CH-[CH2]5=CH2
25
[C (=O )O H ]
20
п‚Ё A s-deposited
пЃ¬ w ater rinsed
пЃ„ hex ane rinsed
15
10
5
0
0 .0
0 .2
0 .4
0 .6
0 .8
P ro p o rtio n o f 1 ,7 o ctad ien e
Alexander, M. R. & Duc, T. M. A study of the interaction of acrylic acid/1,7-octadiene plasma deposits with water and other solvents. Polymer 40, 5479-5488 (1999).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
The solubility of ppAAc
120
Thickness / Г…
100
80
60
40
20
0
0
5
10
P /W
15
20
O verlayer thickness of ppA A c on alum inium after rinsing w ith w ater ( п‚Ё ) and
ethanol (п‚Ў ) versus plasm a deposition pow er, P .
Alexander, M. R. & Duc, T. M. A study of the interaction of acrylic acid/1,7-octadiene plasma deposits with water and other solvents. Polymer 40, 5479-5488 (1999).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Plasma polymer chemical gradients combined with automated small spot XPS:
An efficient method of investigating surface chemistry- adsorbate interactions
Whittle, J. D., Barton, D., Alexander, M. R. & Short, R. D. A method for the deposition of controllable chemical gradients. Chem. Comm., 1766-1767 (2003).
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Immersed in a 5W octadiene-acrylic acid plasma
-drawer retracted and Oct-AAc ratio varied
Whittle, J. D., Barton, D., Alexander, M. R. & Short, R. D. A method for the deposition of controllable chemical gradients. Chem. Comm., 1766-1767 (2003).
Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
XPS C1s core levels
C 1s/17
2
x 10
CPS
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electron
extraction
area
X -ray illu m ination
70
60
50
40
30
20
10
0
Distance/ 0.5
mm steps
290
288
286
284
282
280
Binding Energy (eV)
Printed using CasaXPS
1 m m (F W H M )
0.3
0.7 m m
0.5 m m
пЃ„ E = 0.65
eV m m -1
Whittle, J. D., Barton, D., Alexander, M. R. & Short, R. D. A method for the deposition of controllable chemical gradients. Chem. Comm., 1766-1767 (2003).
Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Co-plasma polymerisation of acrylic acid-octadiene
Acrylic acid
Octadiene
C 1s/27
C 1s
C 1s/117
2
x 10
45
70
40
60
35
50
30
CPS
CPS
CH
40
30
10
Printed using CasaXPS
20
5
X
CO OR C-O
C= OC-COO R
CH
25
10
CO OR
C-COO R
C-O
C=O
0
0
300
2
x 10
15
20
C 1s
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•
290
Binding Energy (eV)
280
300
Printed using CasaXPS
290
Binding Energy (eV)
280
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Co-plasma polymerisation of acrylic acid-octadiene
Trifluoro ethanol derivatisation-stoichiometric reaction
with carboxylic acid functionalities
Acrylic acid
Octadiene
C 1s/140
C 1s/8
2
x 10
2
x 10
80
40
CH
70
35
60
30
50
25
CPS
CPS
CH
40
20
30
15
20
10
10
300
5
C-O X
CO ORC=O
C-cOOR
O-C-cF3
C F3
290
280
300
C F3
O-C-cF3
290
Binding Energy (eV)
Binding Energy (eV)
Printed using CasaXPS
X
C=O C-O
C-cOOR
Printed using CasaXPS
C-C(=O)-OH + CF3-CH2-OH => C- C(=O)-O-CH2- CF3 + H2O
280
Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Co-plasma polymerisation of acrylic acid-octadiene
Trifluoro ethanol derivatisation-stoichiometric reaction
with carboxylic acid functionalities
Acrylic acid
Octadiene
6
100
80
70
4
60
3
50
40
2
30
20
1
10
0
0
0
2
4
6
P o sitio n /m m
8
10
12
co n cen trat io n o f C an d O , at%
90
5
[C O O H ]
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Co-plasma polymerisation of acrylic acid-octadiene
Fluorine, chlorine and bromine substituted epoxides reaction with carboxylic acid functionalities
0.6
0.5
Concentration, at%
F organic
Cl
0.4
Br
0.3
0.2
0.1
0
0
2
4
6
8
10
12
14
Position / mm
Alexander, M. R., Whittle, J. D., Barton, D. & Short, R. D. Plasma polymer chemical gradients for evaluation of surface reactivity: epoxide reaction with carboxylic acid
surface groups. J. Mater. Chem. 14, 408-412 (2004).
Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Co-plasma polymerisation of acrylic acid-octadiene
Fluorine, chlorine and bromine substituted epoxides reaction with carboxylic acid functionalities
0.50
0.45
F , C l, B r co n cen tratio n at%
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F or ganic
Cl
0.40
Br
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0
1
2
3
[C O O H ]
4
5
6
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Functional composition
Reducing adhesion
Promoting adhesion
Chemical gradients
Summary
Gradients of controlled functional concentration can be deposited
- carboxylic acid
- amine
Immobilisation can be achieved though the carboxylic acid functionality
- trifluoro ethanol (stoichiometric)
- halogen substituted epoxides (indicative of reaction of epoxy with
carboxylic acid)
Applications
These gradients and uniform plasma polymer surfaces have be utilised in
studies where cell attachment has been controlled and for structural adhesion
control. A bibliography is provided on the next slide.
Selected publications (involving MR Alexander) on plasma polymers and cells
1. Zelzer, M., Albutt, D., Alexander, M. & Russell, N. The Role of Albumin and Fibronectin in the Adhesion of Fibroblasts to Plasma Polymer
Surfaces. Plasma Processes and Polymers 8 (2012).
2. Zelzer, M. & Alexander, M. Nanopores in Single- and Double-Layer Plasma Polymers Used for Cell Guidance in Water and Protein Containing
Buffer Solutions. Journal of Physical Chemistry B 114, 569–576 (2010).
3. Majani, R., Zelzer, M., Gadegaard, N., Rose, F. R. & Alexander, M. R. Preparation Of Caco-2 Cell Sheets Using Plasma Polymerised Acrylic
Acid As A Weak Boundary Layer. Biomaterials 31, 6764-6771 (2010).
4. Zelzer, M., Majani, R., Bradley, J. W., Rose, F. R. A. J., Davies, M. C. & Alexander, M. R. Investigation of cell–surface interactions using
chemical gradients formed from plasma polymers. Biomaterials 29, 172–184 (2008).
5. Dehili, C., Lee, P., Shakesheff, K. & Alexander, M. Comparison of primary rat hepatocyte attachment to collagen and plasma polymerised
allylamine on glass. Plasmas Processes and Polymers 3, 474–484 (2006).
6. Barry, J., Silva, M., Shakesheff, K., Howdle, S. & Alexander, M. Using Plasma Deposits to Promote Cell Population of the Porous Interior of
Three-Dimensional Poly(D,L-Lactic Acid) Tissue-Engineering Scaffolds. Advanced Functional Materials 15, 1134-1140 (2005).
7. Alexander, M. R., Whittle, J. D., Barton, D. & Short, R. D. Plasma polymer chemical gradients for evaluation of surface reactivity: epoxide
reaction with carboxylic acid surface groups. J. Mater. Chem. 14, 408-412 (2004).
Selected publications (involving MR Alexander) on structural applications of plasma polymers
1. Pinson, S. J. M., Collins, J., Thompson, G. E. & Alexander, M. R. in Aluminium Surface Science and Technology. 448-453 (ATB Metallurgie,
Brussels).
2. Dartevelle, C., McAlpine, E., Thompson, G. E. & Alexander, M. R. Low pressure plasma treatment for improving the strength and durability of
adhesively bonded aluminium joints. Surface and Coatings Technology 173, 249-258 (2003).
3. Pinson, S. J. M., Collins, J., Thompson, G. E. & Alexander, M. R. Atmospheric pressure plasma cleaning of aluminium. Finishing 26, 40-44
(2002).
4. Dinelli, F., Leggett, G. J. & Alexander, M. R. Nanowear in scanning force microscopy: Information on deposits formed in and downstream of a
hexane plasma. Journal of Applied Physics 91, 3841-3846 (2002).
5. Beake, B. D., Zheng, S. & Alexander, M. R. Nanoindentation testing of plasma-polymerised hexane films. Journal of Materials Science 37,
3821-3826 (2002).
6. Beake, B. D., Leggett, G. J. & Alexander, M. R. Characterisation of the mechanical properties of plasma- polymerised coatings by
nanoindentation and nanotribology. Journal of Materials Science 37, 4869-4877 (2002).
7. Pinson, S. J. M., Collins, J., Thompson, G. E. & Alexander, M. R. Atmospheric pressure plasma cleaning of aluminium. Transactions of the
Institute of Metal Finishing 79, 155-159 (2001).
8. Grunkemeier, J. M., Tsai, W. B., Alexander, M. R., Castner, D. G. & Horbett, T. A. Platelet adhesion and procoagulant activity induced by
contact with radiofrequency glow discharge polymers: Roles of adsorbed fibrinogen and vWF. J. Biomed. Mater. Res. 51, 669-679 (2000).
9. Alexander, M. R., Zhou, X., Thompson, G. E., Duc, T. M., McAlpine, E. & Tielsch, B. J. Functionalized plasma polymer coatings for improved
durability of aluminium-epoxy adhesive joints: fractography. Surf. Interface Anal. 30, 16-20 (2000).
Acknowledgements
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Graham Leggett, The University of Sheffield.
Robert Short, The University of Sheffield.
Tran Minh Duc, BIOPHY Research
Graham Beamson, RUSTI, Daresbury.
Neal Fairley, CasaXPS.
Eoghan McAlpine, Alcan International, Banbury
Laboratory.
George Thompson, CPC, UMIST.
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Funding: EPSRC & EU Marie Curie.
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