Article(id=1289306743113101543, tenantId=1146029695717560320, journalId=1287019341717536775, issueId=1289306742370709735, articleNumber=null, orderNo=null, doi=10.3724/j.1000-4734.2025.45.005, pmid=null, cstr=32252.14.j.1000-4734.2025.45.005, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1708358400000, receivedDateStr=2024-02-20, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1785324281718, onlineDateStr=2026-07-29, pubDate=1770652800000, pubDateStr=2026-02-10, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1785324281718, onlineIssueDateStr=2026-07-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1785324281718, creator=13701087609, updateTime=1785324281718, updator=13701087609, issue=Issue{id=1289306742370709735, tenantId=1146029695717560320, journalId=1287019341717536775, year='2026', volume='46', issue='1', pageStart='20', pageEnd='170', issueExtLink='null', onlineDate='null', pubDate='1770652800000', pubDateStr='2026-02-10', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1785324281542, creator='13701087609', updateTime=1785388512677, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1289576147356860923, tenantId=1146029695717560320, journalId=1287019341717536775, issueId=1289306742370709735, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1289576147356860924, tenantId=1146029695717560320, journalId=1287019341717536775, issueId=1289306742370709735, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=41, endPage=48, ext={EN=ArticleExt(id=1289306743272485096, articleId=1289306743113101543, tenantId=1146029695717560320, journalId=1287019341717536775, language=EN, title=Changes of structure and micromorphology of muscovite in the process of its interfacial reaction with acidic solutions, columnId=null, journalTitle=Acta Mineralogica Sinica, columnName=null, runingTitle=null, highlight=null, articleAbstract=

The dissolution of silicate minerals is of great importance to many geochemical processes. In order to better comprehend the dissolution properties of muscovite, the dissolution process of cations, and the changes of structure and microstructure of muscovite in aqueous interfacial reaction with oxalic acid and sulfuric acid solutions have been studied in this paper. The changes of composition, structure and morphology of muscovite in the process of its interfacial reaction with acidic solutions have been characterized by using ICP-OES, XRD, SEM and AFM methods. The results show that the dissolution rates of cations from muscovite in sulfuric acid solution are relatively high, due to the relatively large concentration of H+ in sulfuric acid solution at the initial stage of the reaction. With the progress of the reaction, oxalic acid solution resulted in a rapid dissolution of Si4+, Al3+ and K+ from moscovite. This can be attributed to the weakening of bond energy of moscovite and reduction of the H+ repulsion on the surface of muscovite caused by the adsorption of oxalate anionic ligands on the surface of muscovite. In the reaction process of muscovite with oxalic acid and sulfuric acid solutions, the dissolution rate of K+ is higher than those of Al3+ and Si4+, which is related to the binding force between ions. After the reaction of muscovite with oxalic acid solution, the concentration ratio of dissolved Al3+ and Si4+ (Al/Si value) is increased gradually with the extension of reaction time. However, after the reaction of muscovite with sulfuric acid solution, the Al/Si value is changed in an opposite trend. This difference is due to the fact that the complexation of Al3+ by oxalate anion ligands resulted in the accelerated dissolution of Al3+ in structure of muscovite, while the complexation of Si4+ by oxalate anion ligands resulted in weak influence on the dissolution of Si4+ in structure of muscovite. After the reactions of muscovite with oxalic acid and sulfuric acid solutions, banded corrosion pits appeared on the surface of muscovite, which was related to the preferential dissolution of the defect site of muscovite. The formation of the corrosion pits resulted in the attack of proton and ligand on the exposed new edge surface (hk0), then caused the increase of size of corrosion pit more than the increase of depth.

, authors=Li ZENG, Tongjiang PENG, Hongjuan SUN*, Xiyue ZHANG, Dingran ZHAO, authorsList=Li ZENG, Tongjiang PENG, Hongjuan SUN, Xiyue ZHANG, Dingran ZHAO, authorCompany=null, correspAuthors=Hongjuan SUN, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1289306744824377592, articleId=1289306743113101543, tenantId=1146029695717560320, journalId=1287019341717536775, language=CN, title=白云母与酸性水界面反应过程中结构和微观形貌的变化, columnId=1289306743352176873, journalTitle=矿物学报, columnName=论文, runingTitle=null, highlight=null, articleAbstract=

硅酸盐矿物的溶解反应对于许多地球化学过程具有重要的意义。为了更好地理解造岩矿物白云母的溶解特性,本文研究了白云母与草酸和硫酸溶液的水界面反应中阳离子的溶出过程及结构和微观形貌的变化。采用ICP-OES、XRD、SEM和AFM等手段测试了水界面反应过程中白云母的组分、结构及形貌的变化。研究表明,在反应初期,由于硫酸溶液中H+浓度相对较大,使得白云母在硫酸溶液中的离子溶解速率较大,随着反应的进行,草酸溶液显示出对Si4+、Al3+和K+等离子的快速溶解作用,这可归因于草酸阴离子配体在白云母表面的吸附作用使得键能削弱并降低白云母表面H+排斥性。在白云母与草酸和硫酸溶液反应过程中,K+的溶解速率大于Al3+和Si4+,这与离子之间的结合力有关。白云母与草酸溶液反应后,溶出的Al3+和Si4+浓度比值(Al/Si)随反应时间的延长逐渐增大,而与硫酸溶液反应后Al/Si值的变化呈相反的趋势。这种差异性是由于草酸阴离子配体对Al3+的络合作用加速了白云母结构中Al3+的溶出,而对Si4+的影响较弱导致的。白云母与草酸和硫酸溶液水界面反应后,表面出现条状蚀坑,这与白云母缺陷位点优先溶解有关。蚀坑的形成使得新的边缘面(hk0)暴露于质子和配体的攻击之下,导致蚀坑尺寸增大的程度大于加深的程度。

, authors=曾鹂, 彭同江, 孙红娟*, 张曦月, 赵丁冉, authorsList=曾鹂, 彭同江, 孙红娟, 张曦月, 赵丁冉, authorCompany=null, correspAuthors=孙红娟, authorNote=

曾鹂,女,1996年生,博士研究生,从事矿物材料研究工作。E-mail:

, correspAuthorsNote=
E-mail:
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曾鹂,女,1996年生,博士研究生,从事矿物材料研究工作。E-mail:

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曾鹂,女,1996年生,博士研究生,从事矿物材料研究工作。E-mail:

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journalId=1287019341717536775, articleId=1289306743113101543, language=CN, label=图1, caption=白云母样品与草酸和硫酸溶液水界面反应过程中Si4+(a)、Al3+(b)和K+(c)的溶解量随时间的变化关系图, figureFileSmall=e6+3KMRKNlOAAro9gNjKYA==, figureFileBig=OmDauWqVMJK+vGvhJjvAvg==, tableContent=null), ArticleFig(id=1289306749287117089, tenantId=1146029695717560320, journalId=1287019341717536775, articleId=1289306743113101543, language=EN, label=Fig. 2, caption=Dissolution rate curves of Si4+(a), Al3+(b) and K+(c) with time in the process of interfacial reaction of muscovite with oxalic acid and sulfuric acid solutions, figureFileSmall=4M9nVQghC87wScvv4avJfQ==, figureFileBig=4JarxfzL44N1OAnHKnOK/w==, tableContent=null), ArticleFig(id=1289306749354225954, tenantId=1146029695717560320, journalId=1287019341717536775, articleId=1289306743113101543, language=CN, label=图2, caption=白云母样品与草酸和硫酸溶液水界面反应过程中Si4+(a)、Al3+(b)和K+(c)的溶解速率随时间的变化曲线, figureFileSmall=4M9nVQghC87wScvv4avJfQ==, figureFileBig=4JarxfzL44N1OAnHKnOK/w==, tableContent=null), 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and sulfuric acid solutions, figureFileSmall=pTwi8lIExh4YjYHdgquOYA==, figureFileBig=/v5olx/cDxmg/sVTxcB4bQ==, tableContent=null), ArticleFig(id=1289306749647827238, tenantId=1146029695717560320, journalId=1287019341717536775, articleId=1289306743113101543, language=CN, label=图4, caption=白云母原样及与草酸和硫酸溶液水界面反应300 d产物的XRD图谱, figureFileSmall=pTwi8lIExh4YjYHdgquOYA==, figureFileBig=/v5olx/cDxmg/sVTxcB4bQ==, tableContent=null), ArticleFig(id=1289306751312965927, tenantId=1146029695717560320, journalId=1287019341717536775, articleId=1289306743113101543, language=EN, label=Fig. 5, caption=SEM images of raw muscovite and products after 300 days of the interfacial reaction of muscovite with oxalic acid and sulfuric acid solutions, figureFileSmall=V2NNXjpXMTLEqn5utfV3Yw==, figureFileBig=YR4xd6c6m6SkVr8vUgwmIg==, tableContent=null), ArticleFig(id=1289306751392657704, tenantId=1146029695717560320, journalId=1287019341717536775, articleId=1289306743113101543, language=CN, label=图5, caption=白云母原样及与草酸和硫酸水界面反应300 d产物的SEM图

a. Mus;b. Mus-OA-300;c. Mus-SA-300。

, figureFileSmall=V2NNXjpXMTLEqn5utfV3Yw==, figureFileBig=YR4xd6c6m6SkVr8vUgwmIg==, tableContent=null), ArticleFig(id=1289306751451377961, tenantId=1146029695717560320, journalId=1287019341717536775, articleId=1289306743113101543, language=EN, label=Fig. 6, caption=AFM and corresponding surface height images of raw muscovite and products after 150 and 300 days of the interfacial reaction of muscovite with oxalic acid and sulfuric acid solutions, figureFileSmall=7UGhjbNSaHraM7DWrcYyxw==, figureFileBig=NwtJ7CmCnCINDMu0xh7FbA==, tableContent=null), ArticleFig(id=1289306751514292522, tenantId=1146029695717560320, journalId=1287019341717536775, articleId=1289306743113101543, language=CN, label=图6, caption=白云母原样及与草酸和硫酸水界面反应150和300 d产物的AFM图和对应的表面高度图

a. Mus;b. Mus-OA-150;c. Mus-OA-300;d. Mus-SA-150;e. Mus-SA-300。

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Dissolution rates of Si4+, Al3+ and K+ of muscovite after 300 days of the interfacial reaction of muscovite with oxalic acid and sulfuric acid solutions (%)

, figureFileSmall=null, figureFileBig=null, tableContent=

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Si4+

Al3+

K+

Mus-OA-300

3.77

6.09

6.49

Mus-SA-300

3.32

4.69

6.00

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白云母样品与草酸和硫酸溶液水界面反应300 d后Si4+、Al3+和K+的溶解率(%)

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样品名称

Si4+

Al3+

K+

Mus-OA-300

3.77

6.09

6.49

Mus-SA-300

3.32

4.69

6.00

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Imus002/Iqtz101 ratios of raw muscovite and products after 300 days of the interfacial reaction of muscovite with oxalic acid and sulfuric acid solutions

, figureFileSmall=null, figureFileBig=null, tableContent=

样品名称

Mus

Mus-OA-300

Mus-SA-300

Imus002/Iqtz101

4.858

2.793

3.811

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白云母原样及与草酸和硫酸溶液水界面反应300 d产物的Imus002/Iqtz101

, figureFileSmall=null, figureFileBig=null, tableContent=

样品名称

Mus

Mus-OA-300

Mus-SA-300

Imus002/Iqtz101

4.858

2.793

3.811

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白云母与酸性水界面反应过程中结构和微观形貌的变化
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曾鹂 , 彭同江 , 孙红娟 * , 张曦月 , 赵丁冉
矿物学报 | 论文 2026,46(1): 41-48
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矿物学报 |论文 2026 , 46 (1) : 41 -48
白云母与酸性水界面反应过程中结构和微观形貌的变化
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曾鹂 , 彭同江, 孙红娟* , 张曦月, 赵丁冉
作者信息
  • 西南科技大学 固体废物处理与资源化教育部重点实验室,四川 绵阳 621010
通讯作者:
作者简介:

曾鹂,女,1996年生,博士研究生,从事矿物材料研究工作。E-mail:

Changes of structure and micromorphology of muscovite in the process of its interfacial reaction with acidic solutions
Li ZENG , Tongjiang PENG, Hongjuan SUN* , Xiyue ZHANG, Dingran ZHAO
Affiliations
  • Education Ministry Key Laboratory of Solid Waste Treatment and Resource Recycle, Southwest University of Science and Technology, Mianyang Sichuan 621010, China
出版时间: 2026-02-10 doi: 10.3724/j.1000-4734.2025.45.005
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硅酸盐矿物的溶解反应对于许多地球化学过程具有重要的意义。为了更好地理解造岩矿物白云母的溶解特性,本文研究了白云母与草酸和硫酸溶液的水界面反应中阳离子的溶出过程及结构和微观形貌的变化。采用ICP-OES、XRD、SEM和AFM等手段测试了水界面反应过程中白云母的组分、结构及形貌的变化。研究表明,在反应初期,由于硫酸溶液中H+浓度相对较大,使得白云母在硫酸溶液中的离子溶解速率较大,随着反应的进行,草酸溶液显示出对Si4+、Al3+和K+等离子的快速溶解作用,这可归因于草酸阴离子配体在白云母表面的吸附作用使得键能削弱并降低白云母表面H+排斥性。在白云母与草酸和硫酸溶液反应过程中,K+的溶解速率大于Al3+和Si4+,这与离子之间的结合力有关。白云母与草酸溶液反应后,溶出的Al3+和Si4+浓度比值(Al/Si)随反应时间的延长逐渐增大,而与硫酸溶液反应后Al/Si值的变化呈相反的趋势。这种差异性是由于草酸阴离子配体对Al3+的络合作用加速了白云母结构中Al3+的溶出,而对Si4+的影响较弱导致的。白云母与草酸和硫酸溶液水界面反应后,表面出现条状蚀坑,这与白云母缺陷位点优先溶解有关。蚀坑的形成使得新的边缘面(hk0)暴露于质子和配体的攻击之下,导致蚀坑尺寸增大的程度大于加深的程度。

白云母  /  酸溶液  /  界面反应  /  离子溶出  /  结构演变

The dissolution of silicate minerals is of great importance to many geochemical processes. In order to better comprehend the dissolution properties of muscovite, the dissolution process of cations, and the changes of structure and microstructure of muscovite in aqueous interfacial reaction with oxalic acid and sulfuric acid solutions have been studied in this paper. The changes of composition, structure and morphology of muscovite in the process of its interfacial reaction with acidic solutions have been characterized by using ICP-OES, XRD, SEM and AFM methods. The results show that the dissolution rates of cations from muscovite in sulfuric acid solution are relatively high, due to the relatively large concentration of H+ in sulfuric acid solution at the initial stage of the reaction. With the progress of the reaction, oxalic acid solution resulted in a rapid dissolution of Si4+, Al3+ and K+ from moscovite. This can be attributed to the weakening of bond energy of moscovite and reduction of the H+ repulsion on the surface of muscovite caused by the adsorption of oxalate anionic ligands on the surface of muscovite. In the reaction process of muscovite with oxalic acid and sulfuric acid solutions, the dissolution rate of K+ is higher than those of Al3+ and Si4+, which is related to the binding force between ions. After the reaction of muscovite with oxalic acid solution, the concentration ratio of dissolved Al3+ and Si4+ (Al/Si value) is increased gradually with the extension of reaction time. However, after the reaction of muscovite with sulfuric acid solution, the Al/Si value is changed in an opposite trend. This difference is due to the fact that the complexation of Al3+ by oxalate anion ligands resulted in the accelerated dissolution of Al3+ in structure of muscovite, while the complexation of Si4+ by oxalate anion ligands resulted in weak influence on the dissolution of Si4+ in structure of muscovite. After the reactions of muscovite with oxalic acid and sulfuric acid solutions, banded corrosion pits appeared on the surface of muscovite, which was related to the preferential dissolution of the defect site of muscovite. The formation of the corrosion pits resulted in the attack of proton and ligand on the exposed new edge surface (hk0), then caused the increase of size of corrosion pit more than the increase of depth.

muscovite  /  acidic solutions  /  interfacial reaction  /  ionic dissolution  /  structural evolution
曾鹂, 彭同江, 孙红娟, 张曦月, 赵丁冉. 白云母与酸性水界面反应过程中结构和微观形貌的变化. 矿物学报, 2026 , 46 (1) : 41 -48 . DOI: 10.3724/j.1000-4734.2025.45.005
Li ZENG, Tongjiang PENG, Hongjuan SUN, Xiyue ZHANG, Dingran ZHAO. Changes of structure and micromorphology of muscovite in the process of its interfacial reaction with acidic solutions[J]. Acta Mineralogica Sinica, 2026 , 46 (1) : 41 -48 . DOI: 10.3724/j.1000-4734.2025.45.005
层状硅酸盐矿物的风化对于土壤形成、土壤酸化、碳循环和流域的化学演化具有重要作用[1,2]。层状硅酸盐矿物结构中阳离子的释放有助于调节自然水体的pH,控制着次生矿物相的稳定性和形成、必需营养素的长期供应以及释放潜在的有毒元素[3-5]。为了更好地理解层状硅酸盐矿物的反应活性,需要对其在不同介质下的溶解反应机理进行研究。
白云母是一种TOT型二八面体结构层状铝硅酸盐矿物,其理想结构式为K{Al2[AlSi3O10](OH)2}。八面体片(O)中主要阳离子为Al3+,含少量Mg2+、Fe2+等,Si-O四面体片(T)中主要阳离子为Si4+,少量Al3+代Si4+,通常Si4+/Al3+为3:1,四面体片和八面体片中异价阳离子的类质同象代替导致结构层产生负电荷[6,7]。结构层的负电荷通过在层间域中填充阳离子(主要为K+)平衡。受不同地球化学作用的影响,云母类矿物可产生不同的演化过程,包括转化为其他层状硅酸盐(伊利石、蛭石或蒙脱石)[8-12],反应过程中基面(001)和端面(hk0)也表现出不同的化学反应性。有研究表明,在22~25 °C条件下,云母边缘面的溶解速率比基底面的溶解速率快[13,14];柠檬酸等有机配体可以通过与金属离子的表面络合作用显著影响矿物溶解的动力学和反应机制[15];在草酸和柠檬酸等有机配体存在的条件下,云母的溶解速率比在无配体存在下的溶解速率更快[16,17];溶解过程中质子的促进机制主要通过质子在云母表面的吸附[18]。虽然这些研究报告了云母在不同介质中的不一致溶解,但对白云母在有机酸和无机酸中溶解机制的认识仍然不完整。
为了进一步查明白云母在酸性介质中不同结构位置中阳离子的溶解反应性,本文通过构建草酸和硫酸溶液体系,研究白云母在酸性水溶液中的离子溶解量、溶解速率及结构和微观形貌的变化,以探究白云母的成分释出、结构变化的水界面反应过程与机制。研究成果可为揭示白云母的风化蚀变过程提供理论与实验依据。
原料:白云母样品采自河北省灵寿县,研磨后用蒸馏水连续搅拌24 h进行预洗,抽滤后置于60 ℃烘箱中烘干,研磨过200目筛装袋备用。该白云母样品的化学组成为:SiO2 50.45%,Al2O3 30.04%,K2O 8.61%,Fe2O3 4.37%,Na2O 0.67%,MgO 0.55%,其他1.17%,烧失量4.14%,计算的晶体化学式为:(K0.87Na0.10Ca0.02)0.99{(Al1.67Fe0.25Mg0.05Ti0.04)2.01[(Al1.11Si2.89)4O10](OH)2}。
试剂:草酸(C2H2O4∙2H2O)和硫酸(H2SO4),分析纯,成都科龙化工试剂厂生产;超纯水的电阻率为18.25 ΜΩ∙cm,实验室自制。
1)分别称取4份白云母样品,每份1 g,置于250 mL锥形瓶中,分别加入100 mL 0.1 mol∙L–1的草酸和硫酸溶液及1 mL 0.001 mol∙L–1的叠氮化钠溶液(抑制微生物生长),摇晃锥形瓶,使白云母样品与酸溶液充分接触;2)将锥形瓶置于25 ℃恒温箱中,每隔1 d搅动2 min,使白云母样品与酸溶液充分反应;3)取不同反应时间的反应物上清液5 mL,经0.45 μm微孔过滤器过滤后进行分析,将烧杯中剩余反应物通过恒量中性滤纸过滤使得固液分离,并用去离子水冲洗,直到滤液的电阻率接近蒸馏水,滤渣在60 ℃烘箱中烘干8 h,研磨后备用。样品编号为Mus-XA-t,其中Mus代表白云母样品;XA可为OA和SA,分别表示草酸和硫酸溶液;t为反应时间(d)。
采用日本理学Ultima IV型X射线衍射仪对样品进行物相分析,测试条件:Cu靶,2θ 3°~80°;采用美国Thermo Fisher公司ARL PERFORM`X型X射线荧光光谱仪对样品化学成分进行分析,使用无水四硼酸锂(Li2B4O7)作为熔剂,在1050 ℃熔融制样;采用德国Zeiss仪器公司Ultra 55型场发射扫描电子显微镜对样品进行形貌分析,样品镀金膜;采用日本日立公司5500M型原子力显微镜测定样品的表面形貌及粗糙度;采用美国Thermo Fisher公司Thermo iCAP6500型电感耦合等离子发射光谱仪对滤液进行成分分析,测试条件功率1150 W,泵速50 r/min,辅助气流量0.5 L∙min–1,雾化器气体流量0.55 L∙min–1,冷却气流量12 L∙min–1;采用美国Anton Paar Quanta公司Autosorb IQ比表面积和孔隙度测试仪测试样品的比表面积。
与草酸和硫酸溶液反应t时间后,白云母中离子i的溶解量Si,t(单位为mmol∙g–1)和溶解速率Ri,t(单位为mmol∙d–1∙m–2)分别用公式(1)和公式(2)计算:
Si,t=Ci,tCi,t0Vm0Mi
Ri,t=Si,ttt0viS
式中,Ci,tCi,t0分别为反应t时间和反应t0时间白云母中离子i的溶解浓度(单位为mg∙L–1);V为反应溶液的体积(单位为L);m0为初始白云母质量(单位为g);Mi为离子i的摩尔质量(单位为g∙mol–1);vi为 白云母化学式中i离子的化学计量系数,S为初始白云母样品的比表面积,经测试为 4.947 m2∙g–1t为反应时间(单位为d)。
由白云母样品与草酸和硫酸溶液水界面反应过程中Si4+、Al3+和K+的溶解量随时间的变化关系(图1)可知,在反应300 d内,Si4+和Al3+的溶解达到稳态,而K+仍以较快的速率溶出。这归因于 Si4+和Al3+分别以共价键和离子键与氧结合,在结构中的联结力相对较强,而K+位于层间域,与底氧以弱离子键结合,联结力较弱,易于从结构中溶出[19]。Si4+、Al3+和K+在草酸溶液中的溶解量均大于在硫酸溶液中。其中,Al3+在草酸溶液中的溶解量显著大于在硫酸溶液中的溶解量,这是由于草酸阴离子配体对Al3+的强络合作用降低了溶液中Al3+的有效浓度,导致Al3+的溶解量增加[20,21]表1为白云母样品与草酸和硫酸溶液水界面反应300 d后的溶解率。反应300 d后,离子溶出率的排序为K+>Al3+>Si4+,由此可知,相较于Si4+和Al3+,K+更易于从结构中溶出。
为查明白云母结构中四面体Si4+、八面体Al3+和层间K+的溶解速率,将Si4+、Al3+和K+的溶解速率按初始比表面积及化学式中各元素的化学计量数进行归一化处理,结果如图2所示。白云母结构中的各离子在反应前期的溶解速率较大,这是由于白云母在研磨过程中晶体被解离分散,暴露出新的边缘面和基面导致的。在反应时间为1 d时,硫酸溶液显示出对三种离子的快速溶解,这是由于在相同浓度下,硫酸溶液中的质子浓度高于草酸溶液。随着水界面反应时间的延长,草酸溶液显示出对Al3+和Si4+的快速溶解,这归因于其解离出的阴离子配体对白云母溶解过程的影响。草酸阴离子配体以内球单核双齿方式吸附,使白云母表面的金属–氧键极化,导致键能削弱[22,23],促使表面金属离子易于脱离。在pH为酸性条件下,有机配体的表面吸附还会降低白云母-水界面处的正电荷大小,从而降低表面H+的排斥性,加速溶解反应的进行。
白云母样品与草酸和硫酸溶液水界面反应过程中的Al/Si和K/Si值随时间的变化曲线(图3)表明,在反应过程中,Al/Si和K/Si值均大于白云母的初始化学计量比(0.78和0.24)。这归因于在研磨过程中白云母晶体被劈裂,使边缘位置的八面体Al3+和解理面的K+暴露量增大,从而改变溶解过程中理想的化学计量比。随着反应时间的延长,草酸和硫酸溶液中K/Si值均逐渐减小后趋于稳定。这是由于随着反应的进行,层间剩余K+含量减少所致。随着时间的延长,硫酸溶液中Al/Si值逐渐减小,而草酸溶液中Al/Si值逐渐增大,表明白云母在草酸和硫酸溶液中的溶解机理不同。在反应初始阶段,硫酸溶液中质子浓度相对较大,使白云母中离子快速溶出,且由于Si-O四面体较Al-O八面体稳定,最终使得溶液中Al3+的浓度大于Si4+。随着溶解反应的进行,Al3+溶解速率相对减小使得Al/Si值逐渐减小。而相同浓度的草酸溶液中质子浓度较低,使得初始反应阶段各离子的溶解速率低于硫酸溶液中,但草酸阴离子配体对Al3+具有强络合作用,促使白云母结构中Al3+持续大量地溶出,进而导致了Al/Si值随反应时间的延长逐渐增大。
由白云母原样及与草酸和硫酸溶液水界面反应300 d后产物的XRD图谱(图4)可知,白云母原样中主要矿物相为2M1型白云母(d002=9.8595 Å、d004=4.9987 Å、d006=3.3394 Å和d029=1.9904 Å等),含有少量石英(d100=4.2459 Å和d101=3.3400 Å等)。与草酸和硫酸溶液水界面反应后,白云母的衍射峰峰型和d值没有明显变化,未生成新物相。表2给出了白云母原样及与草酸和硫酸溶液水界面反应300 d产物的002峰与石英的101峰的积分强度比值(Imus002/Iqtz101)。由表2可知,白云母与草酸和硫酸溶液的水界面反应后,Imus002/Iqtz101值有不同程度的减小,且与草酸溶液反应后下降程度更大,表明草酸溶液对白云母结构的破坏作用大于硫酸溶液。
由白云母原样及与草酸和硫酸溶液水界面反应300 d产物的SEM图(图5)可知,白云母原样为15~30 μm的片状颗粒,具有明显的层状结构,表面附着少量细小颗粒。白云母与酸溶液水界面反应300 d后,原样表面的细小颗粒被全部溶解,并出现明显蚀坑,层状边缘由锐利变得平滑。为了进一步研究反应前后蚀坑的变化情况,测试了白云母与草酸和硫酸溶液反应后的AFM图像,结果如图6所示。由图可知,白云母原样表面平整,无明显蚀坑(图6a);与草酸溶液水界面反应150和300 d后,表面出现条状蚀坑,深度分别在5~10和10~20 nm范围内,蚀坑中心深度较边缘大(图6b, c);与硫酸溶液水界面反应150和300 d后出现的条状蚀坑的深度分别在0~5和5~12 nm之间,蚀坑的深度和宽度均小于与草酸溶液反应的样品(图6d, e)。蚀坑的出现与白云母中存在的晶格缺陷有关,包括平面缺陷、点缺陷、边缘和螺旋位错。这些晶体缺陷引起晶格应变并促进位错附近原子优先溶解,溶出的形貌特征可以指示位错的性质[24]。例如,在白云母表面观察到的圆形蚀坑是由点缺陷或成分杂质引起的,而条状蚀坑的形成与c轴取向的螺旋位错有关。蚀坑尺寸增大,表明蚀坑扩散生长比加深更快[14]。从 图6c和6e中可知,蚀坑沿(hk0)方向的扩散溶解的速度较快,而不是沿着(001)面(第二个TOT层)的加深溶解。蚀坑的高度不都是一个TOT层的高度,这是由于未完全溶解的四面体或八面体层的残余物留在表面导致的。
白云母的基面(001)和端面(hk0)反应活性的差异,使得其溶解机制具有一定的差异性和复杂性。一方面,白云母等层状硅酸盐矿物的边缘表面是由高能断键形成的,末端是电价不饱和的氧原子,而在硅氧烷表面上的氧原子是电价饱和的[25]。因此,暴露的端面比基面具有更高的反应活性,更容易被质子攻击。另一方面,白云母基面主要暴露出以共价键结合的Si-O四面体片,稳定性较高,仅有Al代Si位点中的Al3+易于溶出;端面暴露出部分以离子键结合的Al-O八面体,稳定性相对较差,H+可通过与八面体羟基的作用,使得Al3+溶出,促进端面的溶解。此外,与酸溶液反应过程中形成的蚀坑,会加速白云母的溶解。当白云母基底(001)面蚀坑的形成,使得蚀坑新边缘(hk0)面暴露于质子和配体的攻击之下,导致相对于蚀坑加深而言更快地使得蚀坑扩散生长。
基于以上结果,总结了白云母与草酸溶液水界面反应过程(图7)。即在水界面反应过程中,H+沿边缘进入白云母层间,或置换出层间K+等阳离子,或与八面体片的羟基作用形成H2O,使得与羟基配位的Al3+暴露,并脱离结构进入溶液中;H+与四面体片边缘的Si-O(或羟基)作用,使 Si4+以偏硅酸(H2SiO3)的形式进入溶液中,并进一步使Si-O暴露[26];当溶液中存在有机配体时(如草酸根),有机配体在白云母表面的吸附也会也会促使金属离子脱离。随着反应时间的延长,白云母结构的破坏和溶蚀量逐渐增大。
1)白云母与草酸和硫酸溶液的水界面反应未生成新物相,且草酸溶液对白云母结构的破坏作用大于硫酸溶液。
2)在反应初期,白云母在硫酸溶液中的离子溶解速率大于在草酸溶液中,随着反应的进行,草酸溶液显示出对Si4+、Al3+和K+等离子的快速溶解,这可归因于反应初期H+浓度的差异以及草酸根配体对溶解反应的促进作用;相较于硫酸溶液,草酸溶液对白云母结构中阳离子的溶出影响较大。
3)白云母与草酸和硫酸溶液水界面反应后,表面出现条状蚀坑,这与c轴取向的螺旋位错有关。白云母表面缺陷位点的优先溶解造成了蚀坑的形成,进而使得边缘面(hk0)位点暴露量增加,导致溶解进一步进行,并使得蚀坑生长和加深。

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doi: 10.3724/j.1000-4734.2025.45.005
  • 接收时间:2024-02-20
  • 首发时间:2026-07-29
  • 出版时间:2026-02-10
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    西南科技大学 固体废物处理与资源化教育部重点实验室,四川 绵阳 621010

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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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