| 8 | 0 | 10 |
| 下载次数 | 被引频次 | 阅读次数 |
目的:差示扫描量热仪(DSC)的多种校准方法各有优劣，本文研究了不同校准方法之间的差异，为仪器准确校准提供参考。方法:采用熔化焓法和标准比热法对热流型差示扫描量热仪的数据进行校准，对比不同升温速率和不同校准样品质量对两种校准方法获得校准系数的影响。结果:标准比热法在宽温度范围内准确性大于熔化焓法；采用标准比热法和熔化焓法校准后的锡熔化焓相对误差分别为0.79%与5.48%。两种校准方法因升温速率差异产生的变化较小，标准差小于0.01;熔化焓法样品外推温度点与升温速率成正比关系。标准比热法受校准样品质量变化的影响大于熔化焓法，校准时应选择合适的样品质量。在使用标准比热法校准时，通过外推校准物质质量的方式可优化质量差异的影响。结论:研究结果为合理选择差示扫描量热仪的热流校准方法提供了依据，有助于优化仪器的校准过程。
Abstract：Aims: Various calibration methods of differential scanning calorimeters(DSC) have their own advantages and disadvantages. This paper studies the differences among different calibration methods and provides help for instrument calibration. Methods: The melting enthalpy method and the standard specific heat method were employed to calibrate heat flow data obtained by the differential scanning calorimeter. The effects of different heating rates and various calibration sample masses on the calibration coefficients derived from the two methods was compared. Results: The accuracy of the standard specific heat method was higher than that of the melting enthalpy method in a wide temperature range; and the relative errors of tin melting enthalpy calibrated by the standard specific heat method and the melting enthalpy method were 0.79 % and 5.48 %, respectively. The melting enthalpy method and the standard specific heat method had little change due to the difference in heating rate; and the standard deviation was less than 0.01. The extrapolated temperature point of the sample by the melting enthalpy method was proportional to the heating rate. The standard specific heat method was more affected by the mass change of the calibration sample than the melting enthalpy method; and the appropriate sample mass should be selected during calibration. When the standard specific heat method was used for calibration, the influence of mass difference could be optimized by using the method of mass extrapolation of the calibration material. Conclusions: The research results provide a basis for the reasonable selection of the heat flow calibration method of differential scanning calorimeters, which is helpful to the optimization of instrument calibration processes.
[1] 陈咏萱，周东山，胡文兵.示差扫描量热法进展及其在高分子表征中的应用[J].高分子学报，2021,52(3):423-444.CHEN Y X,ZHOU D S,HU W B.Progress in differential scanning calorimetry and its application in polymer characterization[J].Acta Polymerica Sinica,2021,52(4):423-444.
[2] RAJAGUKGUK Y V,ISLAM M,GRYGIER A,et al.Thermal and spectroscopic profiles variation of cold-pressed raspberry seed oil studied by DSC,UV/VIS,and FTIR techniques[J].Journal of Food Composition and Analysis,2023,124:105723.
[3] 吕鹏飞.基于DSC研究酚醛树脂硫化三元乙丙橡胶动力学[J].石油化工，2023,52(5):679-685.LYU P F.Kinetics of ethylene-propylene-diene monomer rubber curing with phenolic resin based on DSC research[J].Chemical Industry,2020,40(8):1494-1502.
[4] LYNCH J M,CORNIUK R N,BRIGNAC K C,et al.Differential scanning calorimetry (DSC):An important tool for polymer identification and characterization of plastic marine debris[J].Environmental Pollution,2024,346:123607.
[5] 吴锐，刘朝霞，黄海伟，等.化学药品标准物质DSC纯度的应用性规律探讨[J].药物分析杂志，2020,40(8):1494-1502.WU R,LIU Z X,HUANG H W,et al.Discussion on the applicable regularity of DSC purity for chemical reference substances[J].Chinese Journal of Pharmaceutical Analysis,2020,40(8):1494-1502.
[6] H?NE G,HEMMINGER W F,FLAMMERSHEIM H J.Differential Scanning Calorimetry[M].Berlin:Springer,2003:1-10.
[7] SARGE S M,GMELIN E,H?NE G,et al.The caloric calibration of scanning calorimeters[J].Thermochimica Acta,1994,247(2):129-168.
[8] SARGE S M,HEMMINGER W,GMELIN E,et al.Metrologically based procedures for the temperature,heat and heat flow rate calibration of DSC[J].Journal of Thermal Analysis,1997(49):1125-1134.
[9] International Union of Pure and Applied Chemistry.Standards calibration,and guidelines in microcalorimetry part 2.calibration standards for differential scanning calorimetry[R].USA:IUPAC,2006.
[10] ASTM.Standard practice for temperature calibration of differential scanning calorimeters and differential thermal analyzers:ASTM E967-18[S].West Conshohocken PA:American Society for Testing Materials,2014.
[11] ASTM.Standard practice for heat flow calibration of differential scanning calorimeters:ASTM E968-2[S].West Conshohocken PA:American Society for Testing Materials,2014.
[12] 国家质量监督检验检疫总局.塑料差示扫描量热法(DSC)第1部分：通则：GB/T 19466.1[S].北京：中国标准出版社，2004.
[13] WUNDERLICH B.Thermal Analysis of Polymeric Materials[M].Berlin:Springer,2005:329-334.
[14] 丁延伟.热分析基础[M].合肥：中国科学技术大学出版社，2020:188-200.
[15] 刘振海，陆立明，唐远望.热分析简明教程[M].北京：科学出版社，2012:27-30.
[16] ASTM.Standard test method for determining specific heat capacity by differential scanning calorimetry:ASTM E1269-11[S].West Conshohocken PA:American Society for Testing Materials,2018.
[17] 中国计量科学研究院.标准物质证书：热分析标准物质[EB/OL].(2021-01-11)[2024-03-05].https://www.ncrm.org.cn/.
[18] 全国物理化学计量技术委员会.示差扫描量热计检定规程：JJG 936-2012[S].北京：中国质检出版社，2013.
[19] 姚涵毅，丁炯，许金鑫，等.塔式热流型差示扫描量热仪研制[J].中国计量大学学报，2021,32(2):210-216,239.YAN H Y,DING J,XU J X,et al.Development of turret-type heat flux differential scanning calorimeters[J].Journal of China University of Metrology,2021,32(2):210-216239.
[20] DITMARS D A,ISHIHARA A,CHANG S S,et al.Enthalpy and heat-capacity standard reference material:Synthetic sapphire(α-AL2O3) from 10 to 2250 K[J].Journal of Research of the National Bureau of Standards,1982,87(2):159-163.
[21] 赵冬梅，李丽霞，郑扬，等.DSC测试中样品内部的温度分布及其对比热测试的影响[J].高分子学报，2012(7):754-758.ZHAO D M,LI L X,ZHENG Y,et al.Temperature distribution in the sample and its effect on the determination of heat capacity on DSC measurements[J].Acta Polymerica Sinica,2012(7):754-758.
基本信息:
DOI：
中图分类号:TH831.1
引用信息:
[1]王临志,许金鑫,胡东芳等.热流型差式扫描量热仪热流校准方法对比分析[J].中国计量大学学报,2025,36(01):1-8+60.
基金信息:
国家重点研发计划项目(No.2023YFF0721903)