熱分析及量熱學1

1、熱分析與量熱學熱分析與量熱學廣西師范大學董家新2022年2月15日熱分析與量熱學熱分析與量熱學l緒論緒論l熱分析和量熱學的熱力學基礎(chǔ)熱分析和量熱學的熱力學基礎(chǔ) l熱分析與量熱學的動力學基礎(chǔ)熱分析與量熱學的動力學基礎(chǔ) l熱分析技術(shù)熱分析技術(shù) l量熱方法和技術(shù)量熱方法和技術(shù) l熱分析和量熱法的應(yīng)用熱分析和量熱法的應(yīng)用 緒論緒論l1 熱分析和量熱學的定義 l2 熱分析和量熱技術(shù)的分類 l3 關(guān)于儀器、測量數(shù)據(jù)和結(jié)果的表述規(guī)范 1. 熱分析和量熱學的定義熱分析和量熱學的定義l熱分析：lThermal Analysis means the analysis of a change in a sample

2、 property, which is related to an imposed temperature alteration.lThermal Analysis: A group of techniques in which a property of the sample is monitored against time or temperature while the temperature of the sample, in a specified atmosphere, is programmed. (國際熱分析與量熱學聯(lián)合會ICTAC)1. 熱分析和量熱學的定義熱分析和量熱學的

3、定義l分析(analysis)說明不只是監(jiān)測，還應(yīng)包括實驗的步驟，和分析、計算所測數(shù)據(jù)的步驟。l樣品的性質(zhì)（property of sample）包括：l熱力學性質(zhì)：溫度、熱量、焓、質(zhì)量、體積等l材料性質(zhì)：硬度、楊氏模量、磁化率等l化學組成或結(jié)構(gòu)。l溫度變化(temperatuer alteration)包括：l溫度步進變化(stepwise change)l線性變化l調(diào)制變化l自由加熱或冷卻l上述方法的組合1. 熱分析和量熱學的定義熱分析和量熱學的定義l特定的氣氛(in a specified atmosphere):特定的壓力壓力：真空 / 高壓 / 常壓，特定的氣體氣體：空氣 / 氮氣

4、/ 氧氣 / 某種反應(yīng)氣體特定的氣體流速流速：不流動 / 以一定的速率流動1. 熱分析和量熱學的定義熱分析和量熱學的定義量熱學：lCalorimetry is the science of measuring the heat of chemical reactions or physical changes.lA general term describing any experiment in which heat is measured as some chemical reaction or physical process occurs.2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分

5、類分類原則：l主分類：根據(jù)所測量的樣品的性質(zhì)來分類l根據(jù)所強調(diào)的內(nèi)容，可進一步進行子分類。主分類子分類熱膨脹2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類lHeating or cooling curve analysis一些重要的熱分析方法一些重要的熱分析方法2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類lDifferential thermal analysis (DTA)2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類lDifferential scanning calorimetry (DSC)Heat flux differential scanning calorimeters

6、Power compensating differential scanning calorimetersMeasured curves and peak directions in DTA and DSCDTA curve with peak representing an endothermic effect.DSC curve with peak representing an endothermic effect.2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類lThermogravimetric analysis (TGA), thermogravimetry (TG)Basic s

7、et-up of a thermobalance.2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類lThermomechanical analysis (TMA)Static force thermomechanical analyzervarious probes for characterizing the mechanical behaviour of the samplePush-rod dilatometer.Modulated force thermomechanical analyzer.2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類lThermomanometric anal

8、ysis 熱壓分析lThermoelectrical analysis 熱電分析lThermomagnetic analysis 熱磁分析lThermooptical analysis (TOA) 熱光分析lThermoacoustic analysis (TAA) 熱聲分析lThermally stimulated exchanged gas analysis (EGA) 熱致氣體交換分析lThermodiffractometric analysis (TDA) 熱衍射分析2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類量熱法的分類標準量熱法的分類標準l(1) 測量的原理 The princ

9、iple of measurementl(2) 操作模式 The mode of operationl(3) 結(jié)構(gòu)原理 The construction principle2 熱分析和量熱技術(shù)的分類熱分析和量熱技術(shù)的分類(1)測量的原理測量的原理 The principle of measurementlheat-compensating principle: 熱補償原理lheat-accumulating principle: 熱累積原理lheat-exchanging principle: 熱交換原理(2)操作模式 The mode of operation (temperature co

10、nditions)static: lisothermal; 等溫lisoperibol; 恒溫環(huán)境 ladiabatic; 絕熱的dynamic: lscanning of surroundings; 環(huán)境溫度掃描lisoperibol scanning; 恒溫環(huán)境溫度，系統(tǒng)溫度掃描ladiabatic scanning. 絕熱掃描(3) 結(jié)構(gòu)原理 The construction principlelsingle measuring system;ltwin or differential measuring system.l分類舉例Heat compensating calorimeter

11、s熱補償式熱量計熱補償式熱量計Ice calorimeterIce calorimeter developed by Lavoisier and Laplace.Heat produced by the animal inside the closed (inner) chamber was measured by the volume of water derived from melted ice cubes, which were placed inside the outer chambers.Adiabatic scanning calorimeterPower compensati

12、ng DSCHeat accumulating calorimeters熱累積式熱量計熱累積式熱量計Drop calorimeterAdiabatic bomb calorimeterIKA C4000Flow calorimeterHeat-exchanging calorimetersHeatflux differential scanning calorimeter (heatflux DSC)Calvet calorimeter3 關(guān)于儀器、測量數(shù)據(jù)和結(jié)果的表述規(guī)范關(guān)于儀器、測量數(shù)據(jù)和結(jié)果的表述規(guī)范 l3.1 儀器的描述General specifications of the mea

13、suring instrumentPerformance characteristics of the measuring system型號溫度范圍氣氛溫度掃描速率樣品類型樣品體積樣品質(zhì)量噪聲重現(xiàn)性線性度時間常數(shù)靈敏度3 關(guān)于儀器、測量數(shù)據(jù)和結(jié)果的表述規(guī)范關(guān)于儀器、測量數(shù)據(jù)和結(jié)果的表述規(guī)范 l3.2 測試曲線和數(shù)據(jù)的描述Sections of the measured curvePeak: 峰Step 臺階Plateau: 平臺Baseline: 基線Isothermal baseline: 等溫基線Initial baseline: 初期基線Final baseline: 末期基線Isoth

14、ermal initial baseline: 等溫起始基線Isothermal final baseline: 等溫終止基線Terms for the evaluation of the measured curvesInterpolated baseline: 內(nèi)插基線Interpolated isothermal baseline: 內(nèi)插等溫基線Extrapolated initial baseline: 外推起始基線Extrapolated final baseline: 外推終止基線Characteristic quantities determined with the aid o

15、f the measured curvePeak height:峰高Peak area: 峰面積Step height: 臺階高度Initial peak/step temperature Ti, 峰/臺階起始溫度Final peak/step temperature Tfin: 峰/臺階終止溫度Extrapolated peak/step onset temperature Te 外推起始溫度Extrapolatedpeak/step completion temperature Tc 外推完成溫度Peak extremum temperature Tp: 峰極值溫度Step midpoin

16、t temperature T1/2: 臺階中點溫度3 關(guān)于儀器、測量數(shù)據(jù)和結(jié)果的表述規(guī)范關(guān)于儀器、測量數(shù)據(jù)和結(jié)果的表述規(guī)范 l3.3 結(jié)果的特性、解釋和展示Characterization of resultsAccuracy 精確度total uncertainty of measurement 完全不確定度Interpretation of results采用多種手段來印證。檢查是否符合熱力學定律測試標準樣品分析測試原理和可能的影響因素對結(jié)果的解釋應(yīng)居于所進行的熱分析和量熱研究。為了支持所做的解釋，可采取以下建議Presentation of measured values, curves and results characterization of the sample, 樣品表征 characterization of the measuring instrtnnent, 儀器表征 calibration procedure, 標定步驟 measuring procedure, 測試步驟 original measurement c