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MSc.

THESIS PROPOSAL

Title of Research

EFFECTS OF DIAZONIUM SALT ON PEEK

By

Name: Muhammad Ahmed Saleem


Registration No: 2013-MS-CH-17

Supervisor

Dr. Saima Yasin


Introduction
The word polymer has its origins in the Greek, polumeres, meaning having many parts.
Polymers are consists of many small molecules called monomers and they linked together to
form macromolecule. Now a days polymers are most widely used as an alternative materials
[1].
Polyetheretherketone (PEEK) is one of best thermoplastic that belongs to a larger family of
polyaryletherketone (PAEK) polymers. Firstly PEEK was contrived by Imperial Chemical
Industries (ICI) below the trade name VICTREX in 1977 [2].The Polyaryletheretherketone
(PEEK) materials are semi-crystalline, high purity polymers comprising of repeating monomers
of two ether groups and a ketone group.
PEEK is a semicrystalline thermoplastic with excellent mechanical and chemical resistance
properties that are retained to high temperatures. The processing conditions used to mold
PEEK can influence the crystallinity, and hence the mechanical properties. The Young's
modulus is 3.6 GPa and its tensile strength 90 to 100 MPa. PEEK has a glass transition
temperature of around 143 C (289 F) and melts around 343 C (662 F). Some grades have a
useful operating temperature of up to 250 C (482 F). The thermal conductivity increases
nearly linearly versus temperature between room temperature and solidus temperature. It is
highly resistant to thermal degradation as well as attack by both organic and aqueous
environments [1, 2].
Diazonium salt, is a class of organic compounds that have the molecular structure, R-N2+-X- ,
in which R is an organic group such as aryl and alkyl and X- is an inorganic and organic anion
such as halogens. Diazonium salts were first obtained from aromatic amines in 1858, and their
utility in the preparation of azo compounds was soon recognized by the dye industry [3].
Diazonium salts are water soluble and they are ionic in nature. These salts usually have a very
stable nitrogen (N2) molecule but at the same time it have highly unstable carbocation that
reacts instantly with nucleophiles for example water. Aromatic diazonium salts are sufficiently
stable but still its ambient temperature not higher than 10 oC.
Diazonium salt are commonly used in surface modification of the metal and polymers, which
enhance the charactertics of the surfaces and these polymers and metal are widely used in
many fields. It has many applications in inks and paints, stents in the medical field, and thin
layers for microelectronics. It is also used in biosensor and in improving fuel cell and Li
batteries electrodes [4].

Problem Statement
PEEK has low elastic modulus similar to bone and considered to be the best substitution of
metallic implants. But the non-treated PEEK is biologically inert, so it has less cellular adhesion
to the biological surfaces, which makes it bio inert [5]. The surface modification and
characterization of PEEK has been a major concern in the recent times.
Research objective
To modify the surface of polymer with deposition of diazonium salt and to analyse the
charactertics of polymer.

Literature Survey
Now a days, Diazonium salt are extensively used in many fields, it has many application in inks
and paints, stents in the medical field, and thin layers for microelectronics. Diazonium salt are
commonly used in surface modification of the metal and polymers, which enhance the
charactertics of the surfaces and these polymers and metal are widely used in many fields [6].
The surface modification of cyclic olefin copolymer with aryldiazonium salt has been reported.
Modify surface can be characterized by fluorescence microscopy and contact angle
measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman
spectroscopy. With the help of diazonium salt the COC modified its wettability, roughness and
the chemical reactivity, which is normally inert.

This diagrams shows the various diazonium layers can enhance the wettability of COC, the
wettability was measured my contact angle. To increase the wettability of COC, it is useful in
medical field and also aryldiazonium salt can bring benefits such as versatile chemical groups
for post-functionalization, low cost and a fast process. This work give the opportunity to
develop biosensor using carboxylated terminated COC surfaces to attach covalently peptide,
protein or NH2 terminated DNA [7].
The grafting of diazonium salts has been used in the biomedical field for the surface
modification of stents. Stents are endovascular devices for treating vascular diseases such as
stenosis of arteries [8].
Modification of PMMA surface with help of the Diazonium salt has been reported. The film of
salt that is attached to PMMA is in the 1-5 nm range. The modified surface is characterized by
IR, XPY and water contact angle. This surface modification permits to control the
hydrophilicity/phobicity of the surface which could be useful for applications where PMMA is
used as a substitute of glass but also to modify to impart specific properties to microfluidic
channels [4].
PEEK has been modify by hydroxyapatite (HA) to make it biocompatible. PEEK is bio inert and
does not integrate well with the surrounding tissues. To solve this problem, chemical
deposition of HA crystalline particles on PEEK substrate. For confirmation, EDX results the
deposition of HA, and the XRD shows that the treated layer was crystalline HA. Similarly FT-IR
analysis show the chemical bonding between HA and substrate Surfaces. The water contact
angle showed an increase in wettability of the treated sample from 71.6 to 36.4 degrees,
which in turn increased its bioactivity [5].

Experimental Methodology
To perform the experiments there are two basic material are used
I. PEEK
II. Diazonium Salt

Methodology
Selection of Polymer
Preparation of Diazonium Salt
Surface activation of Polymer
Deposition of Salt on Polymer
Characterization of Polymer

Selection of polymer
Polymers are used as alternative material to metals and used in many fields due to its
remarkable charactertics. One of the best polymer is polyetheretherketone, widely used in
many fields but the most prominent in medical field. PEEK is commonly used for spinal
implants and in orthopedic, but due its low biocompatibility, diazonium salt is used to improve
its cellular adhesion [9].
Now a days, diazonium salt are used for the surface modifications of many polymers, specially
it is used to enhance the biocompatibility of many polymers, so select two major materials
PEEK and diazonium salt for the experimentations.
Preparation of Diazonium Salt
The diazonium salt will be prepared by following steps
Take 250 ml of beaker, dissolve 5 ml aniline in 16 ml of concentrated HCl and dilute it
with 20 ml water
Cool the temperature of an ice-bath until the temperature has fallen below 5oC
Take 4g of sodium Nitrite(NaNO3)in another beaker with 20 ml water and cool this
solution in the ice-bath
Diazotize the aniline solution by adding NaNO3 solution, in instalment of 2 ml at a time
while stirring the solution continuously and maintain the temperature [4].

Surface activation of polymer


Polymer must be activated, before the salt deposit on polymer, for this purpose, mixture of
two reducing agents hydrochloric acid (0.5M) and hydrophosphorous (H3PO2) are used. Dip
the polymer in the solution and give continuous stirring for 30 minutes.
Another solution are also used HBF4 (50%) and H3PO2 (50%) (50:50 v/v), they also gives the
same results [4].

Deposition of salt on polymer


Polymer are stirred in a solution of containing HCl(.5M) and H3PO2 as a reducing
agent(50:50 v/v), to activate the surface of polymer
Take the polymer and dip in the diazonium salt solution and stir up to 30 min.
Dry the polymer for few hours and then observe the charactertics of polymer [4].

Characterization of polymer
The modified polymeric samples will be analyzed using the following methods

a) Fourier Transform Infrared


FTIR is the method of infrared spectroscopy, in which IR radiation is passed through the
sample. Some of the IR is absorbed by the sample and some of it is passed through. The
resulting spectrum represents the molecular absorption and transmission, creating a
molecular fingerprint of the sample. No two unique molecular structures produce the same
infrared spectrum. This makes infrared spectroscopy useful for several types of analysis.
FTIR gives the information about the sample.
It can identify the unknown materials.
It can determine the quality or consistency of the sample.
It can determine the amount of components in a mixture [10].
b) Thermogravimetric Analysis
It is technique in which the mass of a substance is monitored as a function of temperature or
time as the sample specimen is subjected to a controlled temperature program in a controlled
atmosphere.
TGA helps to determine following quantities.
Determines temperature and weight change of decomposition reactions, which often
allows quantitative composition analysis.
Allows determination of Curie temperatures of magnetic transitions by measuring the
temperature at which the force exerted by a nearby magnet disappears on heating or
reappears on cooling.
Helps to identify plastics and organic materials by measuring the temperature of bond
scissions in inert atmospheres or of oxidation in air or oxygen.
Can determine the purity of a mineral, inorganic compound, or organic material.
Distinguishes different mineral compositions from broad mineral types, such as borax,
boric acid, and silica gels [11].
c) Universal Testing Machine
A universal testing machine is used to test the tensile stress and compressive strength of
materials.it is mostly used in industries for tensile tester, compression tester and bend tester.

d) Scanning Electron Microscope


It is a type of electron microscope that produces images of a sample by scanning it with a
focused beam of electrons. The electrons interact with atoms in the sample, producing
various signals that can be detected and that contain information about the sample's surface.
SEM reveals many information about the samples
Observe surface topography and morphology at high resolution
Measure thin film and coating thickness with calibration standard reference
Measure the size of surface features
Measure particle sizes and determine particle shapes
Determine appearance of stains and residues or deposits on surfaces due to
contamination [12].
Research timetable

Activity Sep Oct Nov Dec Jan Feb

Literature Review

Panel Preparation

Experimentation

Analysis and results

Thesis Write-up
Reference
[1] S. M. Kurtz, An Overview of PEEK Biomaterials, p.^pp. 1-6: William Andrew, 2011.
[2] Y.-W. Du, L.-N. Zhang, Z.-T. Hou, X. Ye, H.-S. Gu, G.-P. Yan, P. Shang, Physical
modification of polyetheretherketone for orthopedic implants, Frontiers of Materials
Science, vol. 8, no. 4, pp. 313-324, 2014.
[3] W. Brock, A History Of Chemistry By Bernadette Bensaude-vincent; Isabelle Stengers;
Deborah Van Dam, p.^pp. 185-186, 1998.
[4] M. M. Chehimi, A. Lamouri, M. Picot, J. Pinson, Surface modification of polymers by
reduction of diazonium salts: polymethylmethacrylate as an example, Journal of
Materials Chemistry C, vol. 2, no. 2, pp. 356-363, 2014.
[5] D. Almasi, S. Izman, M. Assadian, M. Ghanbari, A. Kadir, Crystalline ha coating on peek
via chemical deposition, Applied Surface Science, vol. 314, pp. 1034-1040, 2014.
[6] M. M. Chehimi, Aryl Diazonium Salts: New Coupling Agents and Surface Science, p.^pp.
125: John Wiley & Sons, 2012.
[7] F. Brisset, J. Vieillard, B. Berton, S.-M. Grognet, C.-D. Poc, F.-L. Derf, Surface
functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent
grafting method, Applied Surface Science, vol. 329, pp. 337-346, 2015.
[8] J. A. Belmont, C. Bureau, M. M. Chehimi, S. G. Derouich, J. Pinson, Patents and
industrial applications of aryl diazonium salts and other coupling agents, p.^pp. 5,
2012.
[9] A. H. Poulsson, and R. G. Richards, Surface modification techniques of
polyetheretherketone, including plasma surface treatment, PEEK Biomaterials
Handbook, pp. 145, 2011.
[10] "Introduction to Fourier Transform Infrared Spectrometry," 26th january, 2016;
mmrc.caltech.edu/FTIR/FTIRintro.pdf.
[11] C. R. Anderson. "Thermogravimetric Analysis," 25th january 2016;
http://www.andersonmaterials.com/tga.html.
[12] C. R. Anderson. "Scanning Electron Microscopy," 25th january, 2016;
http://www.andersonmaterials.com/sem.html.
Comments of Supervisor:

Signature of Supervisor Signature of Student


________________________________________________________________________

Endst. No. Univ: ______________ Dated: _____________

The above proposal duly recommended by the Departmental Board of


Studies/Committee of Post-Graduate Studies in its meeting held on _____________ is
forwarded to the Director of Research for obtaining the approval of the Vice-Chancellor.

Dean of Faculty Chairman/Director


Of the Department