Polymers and its characterization

Various characterization techniques of Polymers.

1. POLYMERS AND ITS CHARACTERIZATION Presented by- Siddharth Raju Adsul M.Pharm Sem -I PRN:57400144B Guided by- Prof. Satish Polshettiwar MAEER’S, MAHARASHTRA INSTITUTE OF PHARMACY PUNE - 411038 2016-2017

2. CONTENT INTRODUCTION CLASSIFICATION OF POLYMERS CHARACTERIZATION TECHNIQUES OF POLYMERS CASE STUDY REFERENCES 16-Nov-16 2 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

3. INTRODUCTION Polymers are derived from Greek words, POLY- many & mers - parts of units of high molecular mass, each molecule of which consists of a very large no of single structural units joined together in a regular manner. In other words, Polymers are giant molecules of high molecular weight called macromolecules, which are build up by linking together of a large no of small molecules, called Monomers. Monomers :- The small molecule or repeating units or the building block in the structure of polymer is called monomer. The reaction by which the monomers combine to form polymer is known as Polymerization . Polymerization is a chemical reaction in which 2 or more substances combine together with or without evolution of anything like water, heat or any other solvents to form a molecule of High molecular weight. The product is called Polymer and the starting material is called as monomer. 16-Nov-16 3 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

4. Examples of Polymerisation reaction:- The transformation of ethene to polythene and interaction of hexamethylene diamine and adipic acid leading to the formation of Nylon 6, 6 are examples of two different types of polymerisation reactions. 16-Nov-16 4 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

5. Degree of Polymerisation (DP) :- Number of monomers or repeating unit (n) in the polymer chain is called DP. DP is used to calculate the average molecular weight of Polymer. Average molecular weight of Polymers= DP * Weight of repeating units 16-Nov-16 5 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

6. Classification of Polymers 16-Nov-16 6 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

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10. 16-Nov-16 10 Based on interaction with water :- a ) Non – biodegradable Hydrophobic Polymers : These are inert compounds and are eliminated intact from the site of application. e.g. polyethylene – vinyl acetate, polyvinyl chloride. b) Hydrogels : They swell but do not dissolve when brought in contact with water. e.g. polyvinyl pyrrolidone c) Soluble Polymers : These are moderate mol. wt uncross-linked polymers that dissolve in water. e.g. HPMC, PEG d) Biodegradable Polymers : These slowly disappear from the site of administration in response to a chemical reaction such as hydrolysis. e.g. Polyacrylic acid. Polyglycolic acid. CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

11. 16-Nov-16 11 9. Based on Bio- stability:- a. Bio-degradable polymers - The polymers which gets decomposed under aerobic or anerobic conditions, as a result of the action of micro-organisms/ enzymes. Eg :- Nylon-2, Nylon-6 b. Non-biodegradable polymers - The polymers which contains long chain of carbon and Hydrogen atoms. The interatomic bonding of these molecules is adamant, which makes it tough for microbes to break the bonds and digest them. Eg :- polyethylene, Teflone . CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

12. 16-Nov-16 12 List of characterization techniques of polymers:- X-ray diffraction Infrared spectroscopy Thermal analysis Surface tension/ contact angle surface tension(Surface energy) X-ray photoelectron spectroscopy, XPS Scanning force microscopy SFM Ellipsometry ELLI Infrared attenuated total reflection ATR-FTIR X-ray reflectometry , Grazing incidence x-ray small angle scattering GISAXS Scanning electron microscopy Focused ion beam FIB Electrokinetic measurements/ Zeta potential Inverse Gas chromatography IGC Mechanical properties CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

13. 16-Nov-16 13 1. Tensile strength It is used to determine elastic modulus, ultimate stress, and ultimate strain. Apparatus- It is a dog bone shaped. Sample is placed in the grips of movable & stationary fixtures in a screw driven device. Which pulls the sample until it breaks and measures applied load Vs elongation of the sample. Elongation is typically measured by the extensometer in volts and must be converted to millimeters. Tensile strength testing is a destructive characterization technique. CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

14. 2.X-ray Diffraction 1.It is used to determine the atomic arrangements( i.e. crystal structure) of the material . 2. X-rays (wavelength ≈ 1Å) diffract through a thin polymer sample with long-range order in the arrangement of atoms. 3. The diffracted x-rays yield an interference pattern on a screen or photographic film. 4. Deconvoluting the interference pattern yields spacing between atoms. ( Deconvolution almost always requires sophisticated numerical analysis.) 5. A sample without long-range order ( crystallinity ) will not show an interference pattern. 6. X-rays diffract poorly off hydrogen ; thus, x-ray crystallography does not yield information about the placement of hydrogens (placement must be inferred . 7. Resolution is > 0.1 Å. 16-Nov-16 14 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

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16. 16-Nov-16 16 Identification of semicrystalline polymers and recognition of crystalline phases (polymorphism) of polymers. Fig-A series of wide-angle X-ray diffraction photographs from crystals located along the vertical line within a spherulite of poly(hydroxyl butarate ) shown in the left inset. The enlarged diffractograms are from three areas separated by 60micron meter as shown In the optical micrograph (courtesy of C. Riekel , ESRF). CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

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18. 16-Nov-16 18 3.Infrared spectroscopy The chemical composition & the bonding arrangements of constituents in a homopolymer , copolymer, polymer composite & polymeric materials in general can be obtained using IR spectroscopy. The IR spectroscopy permits the determination of components or groups of atoms that absorb in the infrared at specific frequencies permitting identification of the molecular structure. These techniques are not limited to chemical analysis. In addition the tacticity , crystallinity & molecular strain can also be measured. CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

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20. 4.Ubbelohde & Cannon- Fenske Viscometer:- It is used to determine the viscosity of a liquid polymer. It is a relative method and requires calibration with samples of polymer of known molecular weight. Principle of viscometry is based on Poiseuille's law. 16-Nov-16 20 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

21. 5.Differential Scanning Colorimetry :- It is used to- Identifying unknown polymer. Monitoring effects of aging. Determining phase seperation ( polymer blend, copolymer) Estimating % crystallinity Measuring Heat capacity Determining Thermal stability(oxidation induction time) Determining effects of additives(blends, fillers, plasticizers) Comparing quality(failure analysis, new material evaluation) Determining best processing temperatures(cure, injection molding, extrusion, heat welding) Heat of Fusion Glass transition temperature 16-Nov-16 21 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

22. Principle used in DSC- 16-Nov-16 22 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

23. Differential scanning calorimetry or DSC is a thermo-analytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and reference are maintained at nearly the same temperature throughout the experiment. The sample and a reference substance, which does not undergo a thermal transition in the temperature range of interest, are placed in 2 small metal containers and heated by individual electric heaters. The temperature of both samples, are monitored by thermocouples, is then gradually raised in such a manner that the temperature of sample and reference remain the same. In this way, transition temperatures can be very accurately measured by monitoring the electric current going to the heaters. 16-Nov-16 23 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

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25. 6.Atomic force microscopy(AFM):- The Atomic force microscopy or AFM provides information on structure through nanoscale imaging of topography which is usually acquired in tapping mode. The information obtained from AFM includes morphology, dispersion, domain size, internal structure. Fig-Schematic describing the operation of atomic force microscope 16-Nov-16 25 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

26. 7.X-ray Photoelectron spectroscopy:- It is also known as Electron spectroscopy for chemical analysis(ESCA) Advantages- Surface sensitivity ( 1-10nm sampling depth) Elemental and chemical state identification. Quantitative without the use of standards. Ability to examine highly insulating samples. uses soft X-rays to detach electrons from surfaces Binding Energy of Electron = hν - Emitted electron energy valence electrons ⇒ chemical information core electron ⇒ localized elemental analysis 16-Nov-16 26 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

27. 8.Time of flight-Secondary ion mass spectrometry(TOF-SIMS):- The main attributes are- Surface sensitivity(<0.5nm sampling depth) Elemental and molecular identification Ability to chemically map elements/ molecules on a surface with <1 micrometer image resolution. Ability to examine highly insulating samples. Principle- 16-Nov-16 27 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

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29. 9.Nuclear Magnetic Resonance(NMR):- It is used for- Identifications of the polymers/functional groups Monitor progress of polymerization process Composition Chain molecular structure:type of copolymer Tacticity End groups 16-Nov-16 29 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

30. CASE STUDY-1 CONDUCTIVITY AND DSC STUDIES OF POLY(ETHYLENE GLYCOL) AND ITS SALT COMPLEXES Reference - Indian journal of Engineering and Material sciences Vol-7, October-December 2000, p.p. 456-458 Objective- To determine conductivity and melting range of poly(ethylene glycol) and its salt complexes. Methods- Electrical conductivity is obtained by the standard DC conductivity technique by measuring resistance with the help of Keithley solid state electrometer(model 610) & Melting point of PEG is carried out by DSC in temperature range of 303-343k using T.A. instrument, model- DSC 2010. 16-Nov-16 30 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

31. Results- The doping of PEG with KCL and KBR increases the conductivity about 2.5 times for KCL and 6.25 times for KBR & doping with KI reduces the conductivity to about 0.05 times its pure component value. & Analysis of DSC results confirm that the reaction is endothermic & its melting peak shifts towards the higher value for different salt complexes as compared to PEG. Conclusion- The tempearture response of conductivity may be employed to study the effect of doping on PEG, thereby giving the information on the ionic transport of salt complexes in general and on the structure of these complexes in particular. 16-Nov-16 31 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

32. CASE STUDY-2 Structural Analysis of Ciprofloxacin- Carbopol Polymeric Composites by X-Ray Diffraction and Fourier Transform Infra-Red Spectroscopy. Reference- Tropical Journal of Pharmaceutical Research June 2011; 10 (3): 273-280 Objective- To evaluate physicochemical changes in ciprofloxacin following incorporation in Carbopol polymeric composites. Methods- The ciprofloxacin and Carbopol were mixed in water in a drug:polymer ratio of 1:5 (w/w) and homogenized to produce uniform composites. X-ray powder diffraction analysis of the pure ciprofloxacin and the Carbopol polymeric composites of the drug were obtained using a powder diffractometer . Spectra for the materials were also generated by Fourier transform infrared (FTIR) spectroscope interfaced with an infrared (IR) microscope operated in reflectance mode. 16-Nov-16 32 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

33. Results- Based on the Hanawalt system, three prominent x-ray diffractogram (XRD) peaks of the pure ciprofloxacin and the drug in the polymeric composites exhibited d-spacing at similar 2θ values, but the relative intensity of these peaks was higher in the polymeric composites. FTIR analysis indicates that there were intermolecular hydrogen bonding and esterification between the drug and polymer in the polymeric composites. Conclusion- The changes that occurred in ciprofloxacin indicate increase in stability, decrease in solubility and delayed release of the drug from polymeric composites which could facilitate the formulation of a sustained release form of the drug. 16-Nov-16 33 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

34. BIBLIOGRAPHY:- Ghosh.P , Polymer science & technology, second edition, Tata Mcgraw-Hill , New Delhi,2004, chapter 1,pp-22-39 accessed on 28/10/2016 Daniel L.Cipari , Mechanical characterization of polymer nanocomposites and the role of interphase, Georgia institute of technology, November 2004,pp-1-96 accessed on 30/10/2016 Manfred Stamm , polymer surface and interface characterizationn techniques, Leibniz institute of polymer research Dredson , Springer,Vol-6,2008,pp-1-6accessed on 30/10/2016 Enrique Saldfvar -Guerra & Eduardo vivaldo -Lima, Handbok of polymer synthesis, characterization and processing, John Wiley & Sons,Inc,first edition, 2013, pp-355-366 accessed on 3/11/2016 Rakesh Kumar & Y.K. Agarwal , Analytical Stratigies for characterization of molecular imprinted polymers: A current review, International journal of Chemtech research, vol-6, No-2 , April-June-2014 , pp 1162-1167 accessed on 3/11/2016 16-Nov-16 34 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

35. Rohit Bhargava , Shi-Qing-Wang, Jack L.Koeneg , FTIR microspectroscopy of polymeric systems , Springer ,2003,pp:137-191 Harold P Klug & L R Alexander, X-ray diffraction procedures for polycrystalline & amorphous materials, Wiley-interscience,vol-02,1974,pp-10-19 http://www.intechopen.com/books/infrared-spectroscopy-materials-science-engineering-and -technology accessed on 3/11/2016 www.afmworkshop.com/afm-for-polymer -characterization.html accessed on 3/11/2016 N.Sanjeeva Murthy, Recent developments in polymer characterization using X-ray diffraction, The Rigaku journal, Vol.21/No.1/2004,pp-15-24 accessed on 08/11/16 Turi , Edith A, Thermal characterization of polymeric materials, Academic press,second edition, Vol-1,1997,pp-980 accessed on 8/11/16 R.N.Jagtap & A.H.Ambre , Overview literature on Atomic force microscopy;Basics & its important applications for polymer characterization, Indian journal of Engineering & materials sciences , Vol-13, August 2006, PP-368-384 accessed on 10/11/2016 16-Nov-16 35 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

36. Sergei N Magonov & Darrell H Reneker , Characterization of polymer surfaces with Atomic Force Microscopy,Annu.rev . Mater.sci,vol-27,1997 , pp-175-222 MV Murugendrappa , Syed Khasim & MVN Ambika prasad , Conductivity and DSC studies of Poly( ethyleneglycol ) & its salt complexes, Indian journal of Engineering & material sciences, Vol-7, October-December 2000, pp-456-458 accessed on 14/11/2016 S Sahoo , CK Chakraborti , Structural analysis of ciprofloxacin- carbopol polymeric systems composites by x-ray diffraction & FTIR spectroscopy, Tropical Journal of pharmaceutical research , Vol-10, June 2011, pp-273-280 accessed on 14/11/2016 16-Nov-16 36 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

37. ANY QUESTIONS?????? 16-Nov-16 37 CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

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