R.M. Akhmadullin, R.R. Spiridonova, A.M. Kochnev BASIC AND
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Russian Federation Ministry of Education and Science Federal Agency for Education State Educational Establishment of Higher Professional Education "Kazan National Research Technological University" R.M. Akhmadullin, R.R. Spiridonova, A.M. Kochnev R. Akhmadullin, R. Spiridonova, A. Kochnev BASIC AND APPLIED POLYMER RESEARCH METHODS BASIC AND APPLIED POLYMER RESEARCH METHODS Tutorial Tutorial Kazan KNRTU Kazan, 2012 2012 1 УДК 678.01:53 Основы экспериментальных методов исследования в области полиме- CONTENT ров: Учебное пособие / Р.М. Ахмадуллин, Р.Р. Спиридонова, А.М. Кочнев; Федер. Агенство по образованию, Казан. нац. исслед. технол. 1. ESSENCE OF RESEARCH METHODS 6 ун-т. – Казань: КНИТУ, 2012. – 75с. 1.1 Concepts and Definitions 6 1.2 Scientific Research 6 Рассмотрены основные методы исследования полимеров, применяе- 1.3 Scientific Research Methods 8 мые в отечественной и зарубежной практике. Среди них ядерный 2. CHROMATOGRAPHY METHODS 10 магнитный резонанс, электронный парамагнитный резонанс; инфра- 2.1 Basic Concepts, Terminology 10 красная, рентгеновская, УФ и видимая спектроскопии; хроматография, 2.2 Chromatography Techniques 12 масс-спектрометрия, термогравиаметрические методы анализа, кало- 2.2.1 Chromatographic bed shape 12 риметрия, дилатометрия; оценка стойкости полимеров к внешним воз- 2.2.2 Physical state of mobile phase 14 действиям и эффективности действия стабилизаторов. 2.2.3 Separation mechanism 15 Учебное пособие предназначено для студентов 5 курса полимерного 2.2.4 Special Techniques 16 факультета обучающихся по направлению подготовки 020015 «Хими- 2.3 Chromatograph 18 ческая технология», знакомых с основными понятиями и законами 3. GAS CHROMATOGRAPHY 19 химии и физики высокомолекулярных соединений, методами их син- 3.1 Gas Chromatograph 20 теза, кинетическими и термодинамическими закономерностями поли- 3.2 Qualitative Analysis 21 меризации и поликонденсации, фазовыми и физическими состояниями 3.3 Quantitative Analysis 22 полимеров. Изложенный в учебном пособии материал ознакомит сту- 3.4 Application 22 дентов со спецификой физико-химических методов анализа примени- 4. LIQUID CHROMATOGRAPHY 23 тельно к современным полимерным материалам, а выполнение прак- 4.1 High Performance Liquid Chromatography 23 тических работ на современном оборудовании поможет получить бу- 4.2 Operation 24 дущим дипломированным специалистам навыки работы для дальней- 4.3 Partition Chromatography 26 шего применения в научных и производственных лабораториях. 4.4 Normal-Phase Chromatography 26 4.5 Displacement Chromatography 27 Содержание учебного пособия соответствует программе курса «Осно- 4.6 Reversed-Phase Chromatography 28 вы экспериментальных методов исследования в области полимеров». 4.7 Size-Exclusion Chromatography 30 Рецензенты: 4.8 Ion-Exchange Chromatography 31 Доктор химических наук, 4.9 Thin-Layer Chromatography 32 4.10 Gel Permeation Chromatography 34 Профессор кафедры высокомолекулярных и 5. MASS-SPECTROMETRY 37 элементорганических соединений КФУ И.В. Галкина 5.1 Simplified Example 38 Кандидат химических наук, научный сотрудник 5.2 Creating Ions 39 лаборатории элементорганического синтеза 5.3 Types Of Mass Analyzers 40 ИОФХ им. А.Е. Арбузова КазНЦ РАН А.С. Газизов 5.4 Application 41 6. SPECTROSCOPY 43 6.1 Theory 46 2 3 6.2 Type of Radiative Energy 47 11.3 EPR Methods 86 6.3 Nature of Interaction 47 12. THERMAL ANALYSIS OF POLYMERS 87 6.4 Type of Material 48 12.1 Differential Thermal Analysis 88 7. X-RAY PHOTOELECTRON SPECTROSCOPY 50 12.2 Calorimetry 89 7.1 Physics 52 12.3 Thermogravimetry 91 7.2 Components of an XPS System 52 12.4 Dilatometry 93 7.3 Peak Identification 53 12.5 Thermomechanics 95 7.4 Charge Referencing Insulators 54 12.6 Glass Transition Temperature 99 7.5 Peak-Fitting 55 12.7 Polymer Composition 104 7.6 Application 56 12.8 Instrumentation 105 8. UV and VISIBLE SPECTROSCOPY 56 13. POLYMER DEGRADATION 106 8.1 Beer-Lambert Law 57 13.1 UV Degradation 108 8.2 Ultraviolet-Visible Spectrometer 60 13.2 Thermal Degradation of Polymers 109 8.3 Application 62 13.3 Ozonolysis 110 9. INFRARED SPECTROSCOPY 63 13.4 Stabilizers for Polymers 111 9.1 Sample Preparation 65 BIBLIOGRAPHY 114 9.2 Usual IR Spectrometer Device 66 9.3 IR Spectrometer with Fourier Transforms 68 9.4 Radiation Sources 68 9.5 Detectors 69 9.6 Applications 69 10. NUCLEAR MAGNETIC RESONANCE 70 10.1 Nuclear Spin and Magnets 72 10.2 Values of Spin Angular Momentum 73 10.3 Spin Behavior in a Magnetic Field 73 10.4 Magnetic Resonance by Nuclei 74 10.5 Nuclear Shielding 75 10.6 Relaxation 76 10.7 NMR Spectrometer Diagram 77 10.8 The Classic Description of the NMR Conditions 77 10.9 Chemical Shift 78 10.10 Factors Influencing on the Chemical Shift 79 10.11 Preparation of Samples and Standards for NMR Spectroscopy 80 10.12 NMR Application in Polymer Branch 81 11. ELECTRON PARAMAGNETIC RESONANCE 82 11.1 Origin of an EPR Signal 83 11.2 EPR Method Design 85 4 5 1. ESSENCE OF RESEARCH METHODS sen subject area is advisable. The research will have to be justified by link- ing its importance to already existing knowledge about the topic. Successful characterization of polymer systems is one of the most 2. Hypothesis: A testable prediction which designates the relationship important objectives of today's experimental research of polymers. Consi- between two or more variables. dering the tremendous scientific, technological, and economic importance 3. Conceptual definition: Description of a concept by relating it to of polymeric materials, not only for today's applications but for the industry other concepts. of the 21st century, it is impossible to overestimate the usefulness of expe- 4. Operational definition: Details in regards to defining the variables rimental techniques in this field. Since the chemical, pharmaceutical, medi- and how they will be measured/assessed in the study. cal, and agricultural industries, as well as many others, depend on this 5. Gathering of data: Consists of identifying a population and select- progress to an enormous degree, it is critical to be as efficient, precise, and ing samples, gathering information from and/or about these samples by us- cost-effective in our empirical understanding of the performance of polymer ing specific research instruments. The instruments used for data collection systems as possible. This presupposes our proficiency with, and understand- must be valid and reliable. ing of, the most widely used experimental methods and techniques. 6. Analysis of data: Involves breaking down the individual pieces of 1.1 Concepts and Definitions data in order to draw conclusions about it. Scientific method refers to a body of techniques for investigating 7. Data Interpretation: This can be represented through tables, figures phenomena, acquiring new knowledge, or correcting and integrating pre- and pictures, and then described in words. vious knowledge. 8. Test, revising of hypothesis. 9. Conclusion, reiteration if necessary. Research can be defined as the search for knowledge, or as any systematic investigation, with an open mind, to establish novel facts, solve A common misconception is that a hypothesis will be proven. Gen- new or existing problems, prove new ideas, or develop new theories. erally a hypothesis is used to make predictions that can be tested by observ- ing the outcome of an experiment. If the outcome is inconsistent with the Structure is a fundamental, tangible or intangible notion referring to the recognition, observation, nature, and permanence of patterns and rela- hypothesis, then the hypothesis is rejected. However, if the outcome is con- tionships of entities. sistent with the hypothesis, the experiment is said to support the hypothesis. This careful language is used because researchers recognize that alternative Property is a philosophical category expressing the attitude of the thing to other things it interacts with. hypotheses may also be consistent with the observations. In this sense, a Polymer is any of various chemical compounds made of smaller, hypothesis can never be proven, but rather only supported by surviving identical molecules (called monomers) linked together. rounds of scientific testing and, eventually, becoming widely thought of as true. 1.2 Scientific Research A useful hypothesis allows prediction and within the accuracy of Generally, research is understood to follow a certain structural observation of the time, the prediction will be verified. As the accuracy of process. Though step order may vary depending on the subject matter and observation improves with time, the hypothesis may no longer provide an researcher, the following steps are usually part of most formal research, accurate prediction. In this case a new hypothesis will arise to challenge the both basic and applied: old, and to the extent that the new hypothesis makes more accurate predic- 1. Observations and formation of the topic: Consists of the subject tions than the old, the new will supplant it. Researchers can also use a null area of one’s interest and following that subject area to conduct subject re- hypothesis, which state no relationship or difference between the indepen- lated research. The subject area should not be randomly chosen since it re- dent or dependent variables. A null hypothesis uses a sample of all possible quires reading a vast amount of literature on the topic to determine the gap people to make a conclusion about the population. in the literature the researcher intends to narrow. A keen interest in the cho- 6 7 the effect that the flask type had on the appearance of microorganisms in the soup broth in an effort to study the source of those microorganisms. 1.3 Scientific Research Methods Description: Description is used to gather data regarding natural The goal of the research process is to produce new knowledge, or phenomena and natural relationships and includes observations and mea- deepen understanding of a topic or issue. This process takes three main surements of behaviors. A classic example of a descriptive study is Coper- forms: nicus’s observations and sketches of the movement of planets in the sky in Exploratory research, which structures and identifies new problems.