CN102004084B - Method for measuring contents of ferrous ions and iron ions in glass - Google Patents
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- 239000011521 glass Substances 0.000 title claims abstract description 111
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001448 ferrous ion Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 134
- 229910052742 iron Inorganic materials 0.000 title abstract description 16
- -1 iron ions Chemical class 0.000 title abstract description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 34
- 238000002835 absorbance Methods 0.000 claims abstract description 27
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 21
- 238000012937 correction Methods 0.000 claims abstract description 16
- 238000001228 spectrum Methods 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 34
- 238000009499 grossing Methods 0.000 claims description 8
- 230000003595 spectral effect Effects 0.000 abstract description 33
- 238000012544 monitoring process Methods 0.000 abstract description 6
- 238000000870 ultraviolet spectroscopy Methods 0.000 abstract description 5
- 230000010354 integration Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000009614 chemical analysis method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
本发明公开了一种玻璃中亚铁离子及铁离子的含量测定方法，包括步骤：取玻璃片，利用紫外可见分光光度计测定玻璃片在350～1100nm波段范围内的吸收光谱；将吸收光谱中的吸光度数据除以玻璃片厚度得到单位厚度玻璃片吸光度，进而得到吸收光谱中的波长与单位厚度玻璃片吸光度关系的光谱曲线，对光谱曲线先后进行平滑处理和基线校正；对基线校正后的光谱曲线分别在370nm～400nm波段范围内和520nm～1100nm波段范围内进行面积积分，根据相应的积分面积计算铁离子的含量和亚铁离子的含量。本方法可同时测定亚铁离子及铁离子的含量，操作简单快捷，数据处理简便，可靠性和重复性好，可满足玻璃在线监测的要求，适合工业推广。
The invention discloses a method for measuring the content of ferrous ions and iron ions in glass, comprising the steps of: taking a glass piece, and measuring the absorption spectrum of the glass piece in the range of 350-1100nm by using an ultraviolet-visible spectrophotometer; The absorbance data of the glass sheet is divided by the thickness of the glass sheet to obtain the absorbance of the glass sheet per unit thickness, and then the spectral curve of the relationship between the wavelength in the absorption spectrum and the absorbance of the glass sheet of unit thickness is obtained, and the spectral curve is smoothed and baseline corrected successively; the spectrum after baseline correction The curves were integrated in the range of 370nm-400nm and 520nm-1100nm respectively, and the content of ferric ion and ferrous ion was calculated according to the corresponding integral area. The method can simultaneously determine the content of ferrous ions and ferric ions, has simple and fast operation, simple and convenient data processing, good reliability and repeatability, can meet the requirements of glass on-line monitoring, and is suitable for industrial promotion.
Description
技术领域 technical field
本发明涉及一种玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法。The invention relates to a content determination method of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass.
背景技术 Background technique
铁(Fe)是影响玻璃质量的重要因素。玻璃中的铁有亚铁离子(Fe2+)和铁离子(Fe3+)两种存在形式。亚铁离子(Fe2+)具有很强的着色能力，是影响玻璃白度的主要因素。另外，亚铁离子(Fe2+)能影响玻璃的辐射传热，从而影响玻璃熔窑中玻璃熔体的温度分布。此外，玻璃中亚铁离子(Fe2+)与铁离子(Fe3+)的比例反映了玻璃熔体的氧化还原状态。因此，监测并控制玻璃中亚铁离子(Fe2+)的含量及亚铁离子(Fe2+)与铁离子(Fe3+)的比例是优化玻璃生产工艺的关键因素，对消除玻璃中的气泡、提高玻璃质量具有十分重要的作用。Iron (Fe) is an important factor affecting the quality of glass. Iron in glass exists in two forms: ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ). Ferrous ions (Fe 2+ ) have a strong coloring ability and are the main factor affecting the whiteness of glass. In addition, ferrous ions (Fe 2+ ) can affect the radiation heat transfer of glass, thereby affecting the temperature distribution of the glass melt in the glass melting furnace. In addition, the ratio of ferrous ions (Fe 2+ ) to ferric ions (Fe 3+ ) in the glass reflects the redox state of the glass melt. Therefore, monitoring and controlling the content of ferrous ions (Fe 2+ ) in the glass and the ratio of ferrous ions (Fe 2+ ) to ferric ions (Fe 3+ ) is a key factor in optimizing the glass production process, which is very important for eliminating the ferrous ions (Fe 2+ ) in the glass. Air bubbles and improving glass quality play a very important role.
传统的玻璃中亚铁离子及铁离子含量的测定方法是湿化学分析法，其常采用的原理是：利用氟化氢(HF)和硫酸(H2SO4)将碾细的玻璃粉末溶解成溶液，溶液中的亚铁离子(Fe2+)与邻菲罗啉生成橙红色络合物，在510nm波段处存在稳定的吸收；铁离子(Fe3+)与硫氰酸盐生成血红色络合物，在470nm波段处存在稳定的吸收，通过橙红色络合物与血红色络合物之间的比色可分别测出亚铁离子(Fe2+)和铁离子(Fe3+)的含量。然而，这种湿化学分析法测定操作时间长，亚铁离子(Fe2+)和铁离子(Fe3+)的含量需要分别测定，且由于亚铁离子(Fe2+)在溶液中的不稳定性，故在测定Fe2+含量时一般要进行避光等操作(武文静、颜科，用分光光度-光化学还原测铁法快速测定玻璃的氧化还原度，玻璃纤维，2004，(5)：11～13)，实验操作复杂、实验条件要求高，实验的准确度和精确度因此大打折扣，不能满足玻璃生产中随时监测玻璃氧化还原状态的要求。The traditional determination method of ferrous ion and ferric ion content in glass is wet chemical analysis method, and its commonly used principle is: use hydrogen fluoride (HF) and sulfuric acid (H 2 SO4) to dissolve the finely ground glass powder into a solution, and the solution Ferrous ions (Fe 2+ ) and o-phenanthroline form an orange-red complex with stable absorption at 510nm; iron ions (Fe 3+ ) and thiocyanate form blood-red complexes, There is a stable absorption at the 470nm band, and the contents of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) can be measured respectively through the colorimetry between the orange-red complex and blood-red complex. However, this wet chemical analysis method takes a long time to determine the operation time, and the contents of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) need to be determined separately, and due to the different content of ferrous ions (Fe 2+ ) in the solution Stability, so when measuring Fe 2+ content, it is generally necessary to avoid light and other operations (Wu Wenjing, Yan Ke, using spectrophotometry-photochemical reduction iron method to quickly measure the oxidation-reduction degree of glass, Glass Fiber, 2004, (5) : 11～13), the experimental operation is complicated, the experimental conditions are high, the accuracy and precision of the experiment are greatly reduced, and it cannot meet the requirements of monitoring the redox state of glass at any time in glass production.
侯英兰等报道了利用玻璃原片测定玻璃中亚铁离子(Fe2+)与铁离子(Fe3+)比例的新方法(侯英兰、张贤华、杜震宇，玻璃的氧化还原特性指数变化与玻璃微泡间关系的研究，玻璃，2008，26(2)：22～25)，其根据氧化铁在玻璃中的光谱吸收曲线，建立Fe2+浓度与770nm波段处和1050nm波段处吸光度之差的线性关系标准曲线，以及Fe3+浓度与上述光谱吸收曲线经四次求导后在360～420nm波段范围内最大吸收峰高度的线性关系标准曲线，分别测定玻璃片中的Fe2+含量和Fe3+含量，从而得出亚铁离子(Fe2+)与铁离子(Fe3+)的比例。该玻璃片法克服了上述传统化学分析法中测定操作时间长，Fe2+和Fe3+的含量需分别测定且测定过程受Fe2+不稳定性影响的缺陷，不仅简单快捷，而且满足玻璃生产中随时监测玻璃氧化还原状态的要求。不过，亚铁离子(Fe2+)在400～1100nm波段范围内都有吸收，且随着国际国内市场对深加工玻璃(一般为白玻)质量越来越高的要求，白玻中亚铁离子(Fe2+)的含量将会越来越低，此时单纯根据770nm波段处和1050nm波段处吸光度之差来推断Fe2+含量可能会产生较大的误差。Hou Yinglan et al. reported a new method for measuring the ratio of ferrous ions (Fe 2+ ) to ferric ions (Fe 3+ ) in glass by using original glass sheets (Hou Yinglan, Zhang Xianhua, Du Zhenyu, The relationship between the index change of redox characteristics of glass and the relationship between glass microbubbles Research on the relationship, Glass, 2008, 26(2): 22～25), which established a linear relationship standard between the concentration of Fe 2+ and the difference between the absorbance at 770nm and 1050nm according to the spectral absorption curve of iron oxide in glass Curve, and Fe 3+ concentration and the linear relationship standard curve of the maximum absorption peak height in the range of 360 ~ 420nm after four derivations of the above spectral absorption curve, to measure the Fe 2+ content and Fe 3+ content in glass flakes respectively , so as to obtain the ratio of ferrous ions (Fe 2+ ) to ferric ions (Fe 3+ ). The glass flake method overcomes the shortcomings of the above-mentioned traditional chemical analysis method, such as long measurement operation time, the content of Fe 2+ and Fe 3+ needs to be measured separately, and the measurement process is affected by the instability of Fe 2+ . It is not only simple and fast, but also meets the requirements of glass It is a requirement to monitor the redox state of glass at any time during production. However, ferrous ions (Fe 2+ ) have absorption in the range of 400-1100nm, and with the international and domestic markets increasingly demanding the quality of deep-processed glass (usually white glass), ferrous ions in white glass The content of (Fe 2+ ) will be lower and lower. At this time, the inference of the Fe 2+ content based solely on the difference between the absorbance at the 770nm band and the 1050nm band may produce large errors.
因此，有必要提供一种改进的玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法来克服现有技术的缺陷。Therefore, it is necessary to provide an improved method for determining the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass to overcome the defects of the prior art.
发明内容 Contents of the invention
本发明的目的是提供一种玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法，不仅能克服传统化学分析法的缺陷，测定操作时间短，亚铁离子及铁离子的含量同时测定，测定过程不受亚铁离子不稳定性的影响，满足玻璃生产中随时监测玻璃氧化还原状态的要求，而且能克服侯英兰等提出的玻璃原片测定法的缺陷，亚铁离子(Fe2+)含量测定准确度高。The purpose of the present invention is to provide a method for measuring the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass, which not only can overcome the defects of traditional chemical analysis methods, but also has short measurement operation time, and the ferrous ions and ferric ions (Fe 3+ ) The content of iron ions is measured at the same time, and the determination process is not affected by the instability of ferrous ions, which meets the requirements of monitoring the redox state of glass at any time in glass production, and can overcome the defects of the glass original sheet method proposed by Hou Yinglan et al. The determination accuracy of ion (Fe 2+ ) content is high.
为了实现上述目的，本发明提供了一种玻璃中亚铁离子及铁离子的含量测定方法，包括如下步骤：In order to achieve the above object, the invention provides a method for assaying content of ferrous ions and ferric ions in glass, comprising the steps of:
取玻璃原片，利用紫外可见分光光度计测定玻璃原片在350nm至1100nm波段范围内的吸收光谱；Take the original glass sheet, and measure the absorption spectrum of the original glass sheet in the range of 350nm to 1100nm with a UV-visible spectrophotometer;
将吸收光谱中的吸光度数据除以玻璃原片的厚度得到单位厚度玻璃片吸光度，进而得到吸收光谱中的波长与单位厚度玻璃片吸光度关系的光谱曲线，对光谱曲线先后进行平滑处理和基线校正，以消除仪器噪声对测试数据的影响；Divide the absorbance data in the absorption spectrum by the thickness of the original glass sheet to obtain the absorbance per unit thickness of the glass sheet, and then obtain the spectral curve of the relationship between the wavelength in the absorption spectrum and the absorbance of the glass sheet per unit thickness, and smooth the spectral curve successively. To eliminate the impact of instrument noise on test data;
对基线校正后的光谱曲线在370nm至400nm波段范围内进行面积积分，根据面积积分得到的吸收峰面积计算铁离子的含量，计算公式为：Fe3+(wt％)＝1.104×S370-400nm+2.906×10-2，其中S370-400nm表示单位厚度玻璃片在370nm至400nm波段范围内吸收光谱的吸收峰面积；Perform area integration on the spectral curve after baseline correction within the range of 370nm to 400nm, and calculate the content of iron ions according to the absorption peak area obtained by area integration. The calculation formula is: Fe 3+ (wt%)=1.104×S 370-400nm +2.906×10 -2 , where S 370-400nm represents the absorption peak area of the absorption spectrum of the glass sheet per unit thickness within the range of 370nm to 400nm;
对基线校正后的光谱曲线在520nm至1100nm波段范围内进行面积积分，根据面积积分得到的吸收峰面积计算亚铁离子的含量，计算公式为：Fe2+(wt％)＝7.670×10-3×S520-1100nm+2.011×10-2，其中S520-1100nm是单位厚度玻璃片在520nm至1100nm波段范围内吸收光谱的吸收峰面积。Carry out area integration on the spectral curve after baseline correction within the band range of 520nm to 1100nm, calculate the content of ferrous ions according to the absorption peak area obtained by area integration, the calculation formula is: Fe 2+ (wt%)=7.670×10 -3 ×S 520-1100nm +2.011×10 -2 , where S 520-1100nm is the area of the absorption peak of the absorption spectrum of the glass sheet per unit thickness within the range of 520nm to 1100nm.
与现有技术相比，本发明玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法具有如下优点：Compared with the prior art, the content determination method of ferrous ion (Fe 2+ ) and iron ion (Fe 3+ ) in the glass of the present invention has the following advantages:
1)采用玻璃原片进行测定，操作时间短，可同时测亚铁离子(Fe2+)及铁离子(Fe3+)的含量，测定过程不受亚铁离子(Fe2+)不稳定性的影响，因此实验条件要求低，实验操作简单，能满足玻璃生产中随时监测玻璃氧化还原状态的要求，克服了传统化学分析法的所有缺陷。1) The original glass sheet is used for determination, the operation time is short, and the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) can be measured at the same time, and the determination process is not affected by the instability of ferrous ions (Fe 2+ ) Therefore, the requirements for experimental conditions are low, and the experimental operation is simple, which can meet the requirements of monitoring the redox state of glass at any time in glass production, and overcome all the defects of traditional chemical analysis methods.
2)充分考虑了亚铁离子(Fe2+)在400～1100nm波段范围内的吸收情况，对基线校正后的光谱曲线在520-1100nm波段范围内进行面积积分，进而计算亚铁离子(Fe2+)的含量，Fe2+含量测定误差小，克服了侯英兰等提出的玻璃原片测定法的缺陷。2) Taking full account of the absorption of ferrous ions (Fe 2+ ) in the range of 400-1100nm, the area of the spectral curve after baseline correction is integrated in the range of 520-1100nm, and then the calculation of ferrous ions (Fe 2+ + ) content, Fe 2+ content measurement error is small, overcome the defects of the original glass sheet measurement method proposed by Hou Yinglan et al.
3)整个测试分析过程全部由紫外可见分光光度计和数据处理软件如MS Excel、Origin软件完成，不仅基本消除了人为误差，极大降低了偶然误差，测试数据准确、重复性好，并且数据处理快捷，整个过程不超过12分钟，且由于紫外可见分光光度计成本低、应用普遍，因此本测定方法便于工业推广。3) The entire test and analysis process is completed by UV-Vis spectrophotometer and data processing software such as MS Excel and Origin software, which not only basically eliminates human errors, but also greatly reduces accidental errors. The test data is accurate and repeatable, and data processing It is fast, and the whole process does not exceed 12 minutes, and because the UV-Vis spectrophotometer is low in cost and widely used, the determination method is convenient for industrial promotion.
通过以下的描述并结合附图，本发明将变得更加清晰，这些附图用于解释本发明的实施。The present invention will become clearer through the following description in conjunction with the accompanying drawings, which are used to explain the implementation of the present invention.
附图说明 Description of drawings
图1为本发明玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法的流程图。Fig. 1 is a flow chart of the method for measuring the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass according to the present invention.
图2展示了图1所示玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法中曲线平滑后的光谱曲线。Fig. 2 shows the spectrum curve after the curve is smoothed in the method for determining the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass shown in Fig. 1 .
图3展示了图1所示玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法中基线校正后的光谱曲线。Fig. 3 shows the spectrum curves after baseline correction in the determination method of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass shown in Fig. 1 .
图4展示了图1所示玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法中铁离子(Fe3+)的含量与铁离子(Fe3+)吸收峰积分面积的关系。Figure 4 shows the content of ferrous ions (Fe 3+ ) and the integral of the absorption peak of ferric ions (Fe 3+ ) in the determination method of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in the glass shown in Figure 1 area relationship.
图5展示了图1所示玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法中亚铁离子(Fe2+)的含量与亚铁离子(Fe2+)吸收峰积分面积的关系。 Fig . 5 has shown the content of ferrous ion (Fe 2+ ) and ferrous ion (Fe 2+ ) in the content determination method of ferrous ion (Fe 2+ ) and iron ion (Fe 3+ ) in the glass shown in Fig. 1 The relationship between the integrated area of the absorption peak.
具体实施方式 Detailed ways
现在参考附图描述本发明的实例，附图中类似的元件标号代表类似的元件。Examples of the present invention will now be described with reference to the drawings, in which like reference numerals represent like elements.
本发明玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法的发明人采用纯的化学试剂熔制了一系列不同铁含量的标准玻璃样品，利用邻菲罗啉分光光度法测定标准玻璃样品中的总铁(∑Fe)含量(以Fe2O3表示，单位wt％)，利用硫氰酸铵分光光度法测定标准玻璃样品中铁离子(Fe3+)的含量(以Fe2O3表示，单位wt％)，总铁(∑Fe)含量与铁离子(Fe3+)的含量相减得到亚铁离子(Fe2+)的含量(如表1所示)。通过上述邻菲罗啉分光光度法和硫氰酸铵分光光度法，得到了不同总铁含量的玻璃样品中标准的亚铁离子(Fe2+)含量和铁离子(Fe3+)含量。The inventor of the method for measuring the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass of the present invention melted a series of standard glass samples with different iron contents using pure chemical reagents. Determination of the total iron (∑Fe) content in the standard glass sample by spectrophotometry (expressed as Fe 2 O 3 , unit wt%), using ammonium thiocyanate spectrophotometry to determine the content of iron ions (Fe 3+ ) in the standard glass sample (expressed as Fe2O3 , unit wt%), total iron (∑Fe) content and ferric ion ( Fe3+ ) content are subtracted to obtain ferrous ion (Fe2 + ) content (as shown in Table 1) . The standard ferrous ion (Fe 2+ ) content and ferric ion (Fe 3+ ) content in glass samples with different total iron contents were obtained by the above-mentioned o-phenanthroline spectrophotometric method and ammonium thiocyanate spectrophotometric method.
发明人将上述标准玻璃样品磨成双面抛光、透光率达95％以上的玻璃片，利用紫外可见分光光度计测定了玻璃片在350-1100nm波段范围内的吸收光谱。利用Origin8.0软件将吸收光谱中的吸光度数据除以玻璃片的厚度(单位mm)得到单位厚度玻璃片吸光度，进而得到吸收光谱中的波长与单位厚度玻璃片吸光度关系的光谱曲线，对光谱曲线先后进行曲线平滑(平滑参数选25)和基线校正以消除仪器噪声对测试数据的影响。曲线平滑后的光谱曲线见图2，基线校正后的光谱曲线见图3。The inventor ground the above-mentioned standard glass sample into a glass sheet with double-sided polishing and a light transmittance of over 95%, and measured the absorption spectrum of the glass sheet in the range of 350-1100nm by using an ultraviolet-visible spectrophotometer. Use Origin8.0 software to divide the absorbance data in the absorption spectrum by the thickness of the glass sheet (in mm) to obtain the absorbance of the glass sheet per unit thickness, and then obtain the spectral curve of the relationship between the wavelength in the absorption spectrum and the absorbance of the glass sheet per unit thickness. Curve smoothing (smoothing parameter selection 25) and baseline correction were performed successively to eliminate the influence of instrument noise on the test data. The spectrum curve after curve smoothing is shown in Figure 2, and the spectrum curve after baseline correction is shown in Figure 3.
通过研究不同玻璃样品中亚铁离子(Fe2+)含量和铁离子(Fe3+)含量与每个玻璃样品对应的玻璃片的光谱曲线后发现，玻璃中铁离子(Fe3+)含量与单位厚度玻璃片在370～400nm波段范围内的吸收峰面积(即光谱曲线在370～400nm波段范围内的积分面积)有关，亚铁离子(Fe2+)含量与单位厚度玻璃片在520～1100nm波段范围内的吸收峰面积(即光谱曲线在520～1100nm波段范围内的积分面积)有关。上述各标准玻璃样品单位厚度玻璃片的光谱曲线在370～400nm波段范围内和520～1100nm波段范围内的积分面积见表1。After studying the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in different glass samples and the spectral curves of the glass flakes corresponding to each glass sample, it was found that the content of ferric ions (Fe 3+ ) in glass is related to the unit The thickness of the glass sheet is related to the absorption peak area in the range of 370-400nm (that is , the integrated area of the spectral curve in the range of 370-400nm). It is related to the area of the absorption peak within the range (that is, the integrated area of the spectral curve in the range of 520-1100nm). See Table 1 for the integral areas of the spectral curves of the above-mentioned standard glass samples per unit thickness of the glass sheet in the range of 370-400nm and 520-1100nm.
表1Table 1
在Origin8.0软件中，以光谱曲线在370～400nm波段范围内的吸收峰面积(积分面积)S370～400nm为X轴，Fe3+含量为Y轴，利用Fit Linear命令进行线性拟合，得到如图4所示玻璃中铁离子(Fe3+)含量与光谱曲线在370～400nm波段范围内的吸收峰面积S370～400nm的线性关系，相应的线性回归方程为：In the Origin8.0 software, the absorption peak area (integral area) S 370-400nm of the spectral curve in the range of 370-400nm is taken as the X-axis, and the Fe3 + content is taken as the Y-axis, and the Fit Linear command is used for linear fitting. Obtain the linear relationship between the iron ion (Fe 3+ ) content in the glass and the absorption peak area S 370～400nm of the spectral curve in the range of 370～400nm band as shown in Figure 4, and the corresponding linear regression equation is:
Fe3+(wt％)＝1.104×S370-400nm+2.906×10-2 (1)Fe 3+ (wt%)=1.104×S 370-400nm +2.906×10 -2 (1)
此方程相关系数的平方R2＝0.9973，说明光谱曲线在370～400nm波段范围内的吸收峰面积与Fe3+含量的线性相关性非常好。因此利用光谱曲线在370～400nm波段范围内的吸收峰面积及方程(1)计算得到Fe3+含量可靠性好、准确度高。The square of the correlation coefficient of this equation is R 2 =0.9973, indicating that the linear correlation between the absorption peak area of the spectral curve in the range of 370-400nm and the content of Fe 3+ is very good. Therefore, the Fe 3+ content calculated by using the absorption peak area of the spectral curve in the range of 370-400nm and the equation (1) has good reliability and high accuracy.
在Origin8.0软件中，以光谱曲线在520～1100nm波段范围内的吸收峰面积(积分面积)S520～1100nm为X轴，Fe2+含量为Y轴，利用Fit Linear命令进行线性拟合，得到如图5所示玻璃中亚铁离子(Fe2+)含量与光谱曲线在520～1100nm波段范围内的吸收峰面积S520～1100nm的线性关系，相应的线性回归方程为：In the Origin8.0 software, the absorption peak area (integral area) S 520-1100nm of the spectral curve in the 520-1100nm band is taken as the X-axis, and the Fe2 + content is taken as the Y-axis, and the Fit Linear command is used for linear fitting. Obtain the linear relationship between the ferrous ion (Fe 2+ ) content in the glass and the absorption peak area S 520～1100nm of the spectral curve in the range of 520～1100nm band as shown in Figure 5, and the corresponding linear regression equation is:
Fe2+(wt％)＝7.670×10-3×S520-1100nm+2.011×10-2 (2)Fe 2+ (wt%)=7.670×10 -3 ×S 520-1100nm +2.011×10 -2 (2)
此方程相关系数的平方R2＝0.9966，说明光谱曲线在520～1100nm波段范围内的吸收峰面积与Fe2+含量的线性相关性非常好，因此利用光谱曲线在520～1100nm波段范围内的吸收峰面积和方程(2)计算得到Fe2+含量可靠性好、准确度高。The square of the correlation coefficient of this equation R 2 =0.9966, indicating that the linear correlation between the absorption peak area of the spectral curve in the range of 520-1100nm and the content of Fe 2+ is very good, so using the absorption of the spectral curve in the range of 520-1100nm The Fe 2+ content calculated by peak area and equation (2) has good reliability and high accuracy.
由图4和图5可以看出，两条曲线的线性相关性都很好，相关系数的平方都接近于1，两者相比即可得到亚铁离子(Fe2+)与铁离子(Fe3+)的比值。As can be seen from Figure 4 and Figure 5, the linear correlation of the two curves is very good, and the square of the correlation coefficient is close to 1. By comparing the two, it can be obtained that ferrous ions (Fe 2+ ) and ferric ions (Fe 2+ 3+ ) ratio.
综上所述，本发明玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法包括如下步骤：In summary, the content determination method of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in glass of the present invention comprises the following steps:
步骤S1，取玻璃片，利用紫外可见分光光度计测定玻璃片在350～1100nm波段范围内的吸收光谱；Step S1, taking the glass sheet, and measuring the absorption spectrum of the glass sheet in the range of 350-1100nm with a UV-Vis spectrophotometer;
步骤S2，将吸收光谱中的吸光度数据除以玻璃片的厚度得到单位厚度玻璃片吸光度，进而得到吸收光谱中的波长与单位厚度玻璃片吸光度关系的光谱曲线，对光谱曲线先后进行平滑处理和基线校正，以消除仪器噪声对测试数据的影响；Step S2, divide the absorbance data in the absorption spectrum by the thickness of the glass sheet to obtain the absorbance per unit thickness of the glass sheet, and then obtain the spectral curve of the relationship between the wavelength in the absorption spectrum and the absorbance of the glass sheet per unit thickness, and smooth the spectral curve successively. Calibration to eliminate the influence of instrument noise on test data;
步骤S3，对基线校正后的光谱曲线在370nm至400nm波段范围内进行面积积分，根据面积积分得到的吸收峰面积通过公式(1)计算铁离子的含量；Step S3, performing area integration on the spectral curve after baseline correction within the range of 370nm to 400nm, and calculating the content of iron ions according to the absorption peak area obtained by area integration through formula (1);
步骤S4，对基线校正后的光谱曲线在520nm至1100nm波段范围内进行面积积分，根据面积积分得到的吸收峰面积通过公式(2)计算亚铁离子含量。Step S4, perform area integration on the baseline-corrected spectral curve within the band range of 520nm to 1100nm, and calculate the ferrous ion content according to the absorption peak area obtained by the area integration by formula (2).
下面根据上述原理通过两个实例对本玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法进行详细说明。The method for measuring the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in the glass will be described in detail below by using two examples based on the above principles.
实例一Example one
第一步：取厚度为3.96mm的浮法玻璃片，利用超声波清洗器对其进行清洗，将清洗干净的玻璃片烘干；Step 1: Take a float glass sheet with a thickness of 3.96mm, clean it with an ultrasonic cleaner, and dry the cleaned glass sheet;
第二步：利用紫外可见分光光度计测出玻璃片在350～1100nm波段范围内的吸收光谱，将吸收光谱的数据保存为Excel电子表格文件(扩展名为.xls)；The second step: Utilize the ultraviolet-visible spectrophotometer to measure the absorption spectrum of the glass sheet in the range of 350-1100nm, and save the data of the absorption spectrum as an Excel spreadsheet file (extension: .xls);
第三步：利用数据处理软件如MS Excel、Origin等打开第二步中的电子表格文件(本专利以Origin为例进行说明)，将波长放入X列，吸光度数据放入Y列。选定吸光度列数据，利用set column values函数对吸光度数据除以玻璃片的厚度得到单位厚度玻璃片吸光度，利用Plot-line命令绘图，得到波长与单位厚度玻璃片吸光度关系的光谱曲线，然后利用smoothing命令对光谱曲线进行平滑处理，平滑参数为25，最后对平滑后的光谱曲线进行基线校正；The third step: use data processing software such as MS Excel, Origin, etc. to open the spreadsheet file in the second step (this patent uses Origin as an example), put the wavelength into the X column, and put the absorbance data into the Y column. Select the absorbance column data, use the set column values function to divide the absorbance data by the thickness of the glass sheet to obtain the absorbance per unit thickness of the glass sheet, use the Plot-line command to draw, and obtain the spectral curve of the relationship between the wavelength and the absorbance of the glass sheet per unit thickness, and then use smoothing Command to smooth the spectral curve, the smoothing parameter is 25, and finally perform baseline correction on the smoothed spectral curve;
第四步：利用integrate命令分别对基线校正后的光谱曲线在370～400nm波段范围内和520～1100nm波段范围内进行面积积分，得到铁离子(Fe3+)的积分面积(吸收峰面积)为S370～400nm＝0.02708，得到亚铁离子(Fe2+)的积分面积(吸收峰面积)为Ss20～1100nm＝4.882；Step 4: Use the integrate command to perform area integration on the spectral curve after baseline correction in the range of 370-400nm and 520-1100nm respectively, to obtain the integrated area (absorption peak area) of iron ions (Fe 3+ ) as S 370～400nm =0.02708, the integrated area (absorption peak area) of ferrous ion (Fe 2+ ) is S s20～1100nm =4.882;
第五步：将第四步所得数据分别代入公式(1)和(2)，得Fe2+(wt％)＝0.05756，Fe3+(wt％)＝0.05897，∑Fe(wt％)＝Fe2+(wt％)+Fe3+(wt％)＝0.1165，Fe2+/Fe3+＝0.9761。The fifth step: Substituting the data obtained in the fourth step into formulas (1) and (2) respectively to obtain Fe 2+ (wt%)=0.05756, Fe 3+ (wt%)=0.05897, ΣFe(wt%)=Fe 2+ (wt%)+Fe 3+ (wt%) = 0.1165, Fe 2+ /Fe 3+ = 0.9761.
实例二Example two
第一步：取厚度为1.58mm的高铁玻璃片，利用超声波清洗器对其进行清洗，将清洗干净的玻璃片烘干；Step 1: Take a high-speed iron glass sheet with a thickness of 1.58mm, clean it with an ultrasonic cleaner, and dry the cleaned glass sheet;
第二步：利用紫外可见分光光度计测出玻璃片在350～1100nm波段范围内的吸收光谱，将吸收光谱的数据保存为Excel电子表格文件(扩展名为.xls)；The second step: Utilize the ultraviolet-visible spectrophotometer to measure the absorption spectrum of the glass sheet in the range of 350-1100nm, and save the data of the absorption spectrum as an Excel spreadsheet file (extension: .xls);
第三步：利用数据处理软件如MS Excel、Origin等打开第二步中的电子表格文件(本专利以Origin为例进行说明)，将波长放入X列，吸光度数据放入Y列。选定吸光度列数据，利用set column values函数对吸光度数据除以玻璃片的厚度得到单位厚度玻璃片吸光度，利用Plot-line命令绘图，得到波长与单位厚度玻璃片吸光度关系的光谱曲线，然后利用smoothing命令对曲线进行平滑处理，平滑参数为25，最后对平滑后的曲线进行基线校正；The third step: use data processing software such as MS Excel, Origin, etc. to open the spreadsheet file in the second step (this patent uses Origin as an example), put the wavelength into the X column, and put the absorbance data into the Y column. Select the absorbance column data, use the set column values function to divide the absorbance data by the thickness of the glass sheet to obtain the absorbance per unit thickness of the glass sheet, use the Plot-line command to draw, and obtain the spectral curve of the relationship between the wavelength and the absorbance of the glass sheet per unit thickness, and then use smoothing Command to smooth the curve, the smoothing parameter is 25, and finally perform baseline correction on the smoothed curve;
第四步：利用integrate命令分别对基线校正后的光谱曲线在370～400nm波段范围内和520～1100nm波段范围内进行面积积分，得到铁离子(Fe3+)的积分面积(吸收峰面积)为S370～400nm＝0.2408，得到亚铁离子(Fe2+)的积分面积(吸收峰面积)为S520～1100nm＝37.800；Step 4: Use the integrate command to perform area integration on the spectral curve after baseline correction in the range of 370-400nm and 520-1100nm respectively, to obtain the integrated area (absorption peak area) of iron ions (Fe 3+ ) as S 370~400nm =0.2408, the integrated area (absorption peak area) of ferrous ion (Fe 2+ ) is S 520~1100nm =37.800;
第五步：将第四步所得数据分别代入公式(1)和(2)，得到Fe3+(wt％)＝0.2950，Fe2+(wt％)＝0.3100，∑Fe(wt％)＝Fe2+(wt％)+Fe3+(wt％)＝0.6050，Fe2+/Fe3+＝1.051。The fifth step: Substituting the data obtained in the fourth step into formulas (1) and (2) respectively to obtain Fe 3+ (wt%)=0.2950, Fe 2+ (wt%)=0.3100, ΣFe(wt%)=Fe 2+ (wt%)+Fe 3+ (wt%) = 0.6050, Fe 2+ /Fe 3+ = 1.051.
由上可知，本发明玻璃中亚铁离子(Fe2+)及铁离子(Fe3+)的含量测定方法具有如下优点：As can be seen from the above, the content determination method of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) in the glass of the present invention has the following advantages:
1)采用玻璃原片进行测定，操作时间短，可同时测亚铁离子(Fe2+)及铁离子(Fe3+)的含量，测定过程不受亚铁离子(Fe2+)不稳定性的影响，因此实验条件要求低，实验操作简单，能满足玻璃生产中随时监测玻璃氧化还原状态的要求，克服了传统化学分析法的所有缺陷。1) The original glass sheet is used for determination, the operation time is short, and the content of ferrous ions (Fe 2+ ) and ferric ions (Fe 3+ ) can be measured at the same time, and the determination process is not affected by the instability of ferrous ions (Fe 2+ ) Therefore, the requirements for experimental conditions are low, and the experimental operation is simple, which can meet the requirements of monitoring the redox state of glass at any time in glass production, and overcome all the defects of traditional chemical analysis methods.
2)充分考虑了亚铁离子(Fe2+)在400～1100nm波段范围内的吸收情况，对基线校正后的光谱曲线在520～1100nm波段范围内进行面积积分，进而计算亚铁离子(Fe2+)的含量，Fe2+含量测定误差小，克服了侯英兰等提出的玻璃原片测定法的缺陷。2) Taking full account of the absorption of ferrous ions (Fe 2+ ) in the range of 400-1100nm, the area of the spectral curve after baseline correction is integrated in the range of 520-1100nm, and then the calculation of ferrous ions (Fe 2+ + ) content, Fe 2+ content measurement error is small, overcome the defects of the original glass sheet measurement method proposed by Hou Yinglan et al.
3)整个测试分析过程全部由紫外可见分光光度计和数据处理软件如MS Excel、Origin软件完成，不仅基本消除了人为误差，极大降低了偶然误差，测试数据准确、重复性好，并且数据处理快捷，整个过程不超过12分钟，由于紫外可见分光光度计成本低、应用普遍，因此本测定方法便于工业推广。3) The entire test and analysis process is completed by UV-Vis spectrophotometer and data processing software such as MS Excel and Origin software, which not only basically eliminates human errors, but also greatly reduces accidental errors. The test data is accurate and repeatable, and data processing It is fast, and the whole process does not exceed 12 minutes. Since the ultraviolet-visible spectrophotometer is low in cost and widely used, the determination method is convenient for industrial promotion.
以上结合最佳实施例对本发明进行了描述，但本发明并不局限于以上揭示的实施例，而应当涵盖各种根据本发明的本质进行的修改、等效组合。The present invention has been described above in conjunction with the best embodiments, but the present invention is not limited to the above-disclosed embodiments, but should cover various modifications and equivalent combinations made according to the essence of the present invention.
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1813181A (en) * | 2003-06-24 | 2006-08-02 | 康宁股份有限公司 | Methods for quantifying the oxidation state of glass |
| CN1712932A (en) * | 2004-06-25 | 2005-12-28 | 中国洛阳浮法玻璃集团有限责任公司 | Test for Fe2+ and Fe3+ content in glass |
| CN1712933A (en) * | 2004-06-25 | 2005-12-28 | 中国洛阳浮法玻璃集团有限责任公司 | Test for Fe2+ and Fe3+ content in thin/super-thin glass |
Non-Patent Citations (2)
| Title |
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| 郭冉冉 等.浮法玻璃中 Fe 含量测定方法.《建材世界》.2009,第30卷(第1期),10-15. * |
| 鲁鹏.玻璃中Fe2+和Fe3+测试方法的Tobit模型估计.《玻璃》.2009,(第216期),6-9. * |
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| CN102004084A (en) | 2011-04-06 |
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