硅酸盐学报

基于热重-质谱量化分析的矿渣解离-沉淀-自然碳化过程

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张哲 ¹ , 朱效宏 ¹^,² , 吕昭秋 ¹ , 栾明昱 ¹ , 杨凯 ¹

硅酸盐学报 | 研究论文 2024,52(11): 3554-3564

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硅酸盐学报 |研究论文 2024 , 52 (11) : 3554 -3564

基于热重-质谱量化分析的矿渣解离-沉淀-自然碳化过程

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张哲¹, 朱效宏¹^,², 吕昭秋¹, 栾明昱¹, 杨凯¹

作者信息

^1．重庆大学材料科学与工程学院，重庆 400045，中国

^2．加州大学伯克利分校土木与环境工程学院，CA 94720，美国

通讯作者:

杨凯（1982—），男，博士，副研究员。

作者简介:

张哲（1998—），男，硕士研究生。

Quantitative Thermogravimetric-Mass Spectrometric Analysis of the Dissociation-Precipitation-Natural Carbonation Process of Granulated Blast Furnace Slag

Zhe ZHANG¹, Xiaohong ZHU¹^,², Zhaoqiu LYU¹, Mingyu LUAN¹, Kai YANG¹

Affiliations

^1.College of Materials Science and Engineering, Chongqing University, Chongqing 400045, China

^2.Department of Civil and Environmental Engineering, University of California Berkeley, Berkeley, CA 94720, United States

Corresponding Author:

YANG Kai (1982‒), male, Ph.D., Associate Professor. E-mail: yang.kai@cqu.edu.cn

ZHANG Zhe (1998‒), male, Master candidate. E-mail: zhang.zhe@stu.cqu.edu.cn

出版时间: 2024-11-20 doi: 10.14062/j.issn.0454-5648.20230901

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摘要

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水泥水化后所得到的是多相复合产物，仅采用热重法难以对重叠部分产物实现精准定量。采用热重-质谱联合技术对不同储存湿度条件、不同解离温度条件下的矿渣解离-沉淀-自然碳化过程进行研究，并对矿渣混凝土主要水化非晶产物C-（A）-S-H凝胶、碳化晶体产物CaCO₃等进行量化分析。结果表明：热重-质谱联用技术能准确剥离在热重分析时所得出的样品重叠峰（如C-（A）-S-H凝胶失水峰、不同晶型CaCO₃分解峰等），可有效降低样品在热重定量分析时所造成的物相重叠损失。

关键词

矿渣 / 碳化分析 / 热重分析 / 质谱量化分析

Abstract

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Introduction:

Thermogravimetry (TG) is widely used to evaluate the hydration process and the degree of reaction of cementitious materials. However, it is still challenging to accurately quantify the overlaps of hydration products using TG alone because cement hydration produce complex and multiphase composites. Mass spectrometry (MS) with its high specificity, sensitivity and fast testing speed, can promote TG quantification by eliminating overlapping decomposition peaks, further achieving the accurate quantification of cementitious hydration products. Therefore, this study designed the exposure conditions with different temperatures (5, 20, and 40 ℃) and humidity levels (RH ≈ 33%, RH ≈ 59%, and RH ≈ 95%) to study a dissolution process of the hydrated granulated blast furnace slag (GGBS). Hydration products at 6 different periods of dissolution (5, 10, 20, 30, 60 min, and 120 min) were analyzed to assess the applicability and feasibility of the TG-MS coupling technique for quantifying the early reaction products of GGBS.

Methods:

Granulated blast furnace slag (GGBS) was used in dissolution-carbonation experiments, using deionized water and the 4 mol/L NaOH solution as solvents. The liquid-solid ratio was 50∶1, and the dissolution temperatures were set at 5, 20 ℃, and 40 ℃. Three ambient relative humidity (RH) (33%, 59% and 95%) were controlled using saturated MgCl₂, NaBr, and KNO₃ solutions. Mechanical stirring was performed at 750 r/min, and the vessel was covered with parafilm throughout the dissolution process. The samples were taken at 5, 10, 20, 30, 60 min, and 120 min. The precipitated products were hydration-stopped using the solvent-exchange method, followed by carbonation in a CO₂ concentration of 600 × 10^-6 for 28 d. Water and carbon dioxide were detected using a TG-MS system.

Results and discussion:

The C-(A)-S-H thermal decomposition mass loss in TG correlated well with the H₂O signal in the MS system under tested conditions, whereas the relation depends on degree of hydration. This phenomenon may be attributable to the following factors: on the one hand, it is due to the overlapping peaks observed in the thermogravimetric loss curve affected by water vapor mass loss released by C-(A)-S-H decomposition and heat absorption peaks of the dehydration of loss-combined water in the hydrotalcite-like phases (Mg-Al-LDH). On the other hand, it is related to the partial-pressure system in the MS system that was constantly changing during the gas release. In the quantitative analysis of CaCO₃, the samples with different degrees of hydration exhibited disparate degrees of carbonation, indicating that the degree of hydration influenced the degree of carbonation. Notably, CaCO₃ quantification (expressed as the amount of CO₂ detected) presents different correlations, and there is also a correlation in the quantitative analysis of C-(A)-S-H gel. With the increased hydration (temperature and time), the amount of C-(A)-S-H gel increased, resulting in more CaCO₃ generated by carbonation. Since the decomposition of the C-(A)-S-H gel occurred throughout the entire heating process, an overlap between the decomposition curves of C-(A)-S-H and CaCO₃ should be taken into account. However, the current study did not fully account for gas partial pressures, which led to multiple linear relationships in the correlations within the TG-MS system. This phenomenon can be quantified and calibrated using equivalent characteristic spectrum analysis (ECSA).

Conclusions:

TG-MS was used to analyze the dissolution-precipitation-natural carbonation products of GGBS under several storage humidity and temperature conditions. This method enabled the quantitative description of the amorphous hydration product C-(A)-S-H gel and the crystalline product CaCO₃. The degree of GGBS hydration and natural carbonation varies depending on the dissolution environment (storage humidity, dissociation temperature, and dissolution time), and these processes exhibit a positive correlation between mass loss and MS quantification. Using MS helps to separate overlapping peaks in the TG quantitative process, serving as a complementary and validation method for thermogravimetric analysis. However, when using the TG-MS system for correlation analysis, experimental errors may occasionally arise due to the inherent inaccuracies of TG, the amount of gas within the TG-MS system, and the presence of multiple gases.

Key words

slay / carbonation / thermogravimetric / quantitative mass spectrometric analysis

引用本文

张哲, 朱效宏, 吕昭秋, 栾明昱, 杨凯. 基于热重-质谱量化分析的矿渣解离-沉淀-自然碳化过程. 硅酸盐学报, 2024 , 52 (11) : 3554 -3564 . DOI: 10.14062/j.issn.0454-5648.20230901

Zhe ZHANG, Xiaohong ZHU, Zhaoqiu LYU, Mingyu LUAN, Kai YANG. Quantitative Thermogravimetric-Mass Spectrometric Analysis of the Dissociation-Precipitation-Natural Carbonation Process of Granulated Blast Furnace Slag[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (11) : 3554 -3564 . DOI: 10.14062/j.issn.0454-5648.20230901

基金

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国家自然科学基金(52378218)

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2024年第52卷第11期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230901

接收时间：2023-11-23
首发时间：2026-10-22
出版时间：2024-11-20

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出版历史

收稿日期：2023-11-23
修回日期：2024-02-22

基金

国家自然科学基金(52378218)

作者信息

^1．重庆大学材料科学与工程学院，重庆 400045，中国

^2．加州大学伯克利分校土木与环境工程学院，CA 94720，美国

通讯作者:

杨凯（1982—），男，博士，副研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230901

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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