玉皇庙山戎墓土遗址的盐分调查研究

玉皇庙山戎墓土遗址中可溶-微溶盐导致的遗址表面酥碱、起甲、泛白和块状脱落等病害较为严重。本文利用X射线荧光光谱(XRF)、离子色谱(IC)、X射线光电子能谱(XPS)、X射线衍射仪(XRD)以及透射电镜(TEM)等分析方法测定了玉皇庙山戎墓土遗址不同位置取样点及距遗址表面及不同深度处样品中可溶盐的成分及含量,并分析了盐分对遗址的破坏可能机制。结果表明,该遗址的样品中主要的可溶盐是Na_2Ca(SO_4)_2、Na_2SO_4、NaCl,微溶盐主要是CaSO_4和CaSO_4·2H_2O,此外还含有少量的CaCl_2·6H_2O、KNO_3、KCl、MgCl_2、K_2SO_4和MgSO_4等。随着取样深度增加,样品中各盐分的种类及含量有所减少,此种分布规律可能与可溶盐的赋存环境及水分运移有关。这些结果对于玉皇庙山戎墓土遗址的保护具有一定的参考价值。     

三门峡虢季墓遗址盐害分析与调查

针对三门峡虢季墓遗址部分区域存在起甲、泛白、疱疹等由可溶盐引起的病害,在其遗址不同部位取样进行土遗址本体含盐分析.取样区域包括虢季墓、梁姬墓和近代墓遗址.采用X射线荧光光谱(XRF)和离子色谱(IC)分析所取样品的可溶盐成分、含量及可溶盐成盐元素在土遗址中的成盐规律.采用电子能谱(XPS)和X射线衍射(XRD)分析样品的物相组成及盐分状态,扫描电子显微镜/能谱(SEM/EDS)进一步考察含盐土质的颗粒组成、微观形貌等.结果表明:虢季墓取样区域所含盐分主要为Na_2SO_4、CaCO_3和少量的其他盐分如CaCl_2、KNO_3和NaCl等.靠近地面部位所取样品盐分含量高于其他部位,盐害表现更为明显.梁姬墓取样区域总盐分含量略高于虢季墓与近代墓,硝酸盐含量较高.而近代墓遗址可溶盐盐分含量略低,盐害不明显.在不同取样点可溶盐含量有所差异,但在邻近区域,其成盐具有一定规律性,这一点对于遗址基体中盐害的深入研究与防治具有重要意义.     

Na~+,K~+,Mg~(2+)∥Cl~-,SO_4~(2-)-H_2O五元体系35℃介稳相图研究

研究得出 (Na+ ,K+ ,Mg2 +∥ Cl-,SO2 -4 -H2 O)五元体系 3 5℃时的介稳溶解度数据 ,绘制了该体系 3 5℃的介稳相图 ,共有 9个为氯化钠所饱和的结晶区域 :氯化钾、钾芒硝 (3 K2 SO4 · Na2 SO4 )、钾镁矾 (K2 SO4· Mg SO4 · 4 H2 O)、钾盐镁矾 (KCl· Mg SO4 · 2 .75H2 O)、光卤石 (KCl· Mg Cl2 · 6H2 O)、白钠镁矾 (Na2 SO4· Mg SO4 · 4 H2 O)、硫酸钠、六水硫酸镁 (Mg SO4 · 6H2 O)和水氯镁石 (Mg Cl2 · 6H2 O) .所得 3 5℃介稳相图与 Van t Hoff2 5℃稳定相图比较有较大区别 :软钾镁矾 (K2 SO4 · Mg SO4 · 6H2 O)、七水硫酸镁、五水硫酸镁及四水硫酸镁结晶区域消失 ,钾镁矾和钾盐镁矾结晶区域显著扩大 .所得 3 5℃介稳相图与 2 5℃介稳相图区别很大 :软钾镁矾和七水硫酸镁结晶区域消失 ,同时出现了钾镁矾和钾盐镁矾的结晶区域 .在该五元体系 3 5℃介稳相平衡研究中发现析出的是钾盐镁矾的低水化合物 (KCl·Mg SO4 · 2 .75H2 O)     

298.16K时Na~ ,Mg~(2 )//Cl~-,SO_4~(2-),NO_3~-,H_2O体系中NaCl饱和区域相平衡

采用等温溶解平衡法研究了五元体系Na ,Mg2 //Cl-,SO42-,NO3-,H2O在298.16K下氯化钠饱和平衡体系的溶解度,获得了相应的投影干盐图、氯图和水图.研究结果表明,在298·16K下氯化钠饱和时,该五元体系投影干盐图由8个二盐共饱和的双变面、13条三盐共饱的单变线和6个四盐共饱的零变点构成,存在两种复盐,8个二盐共饱双变面分别对应于NaCl NaNO3,NaCl Na2SO4,NaCl MgCl2·6H2O,NaCl MgSO4·Na2SO4·4H2O,NaCl Mg(NO3)2·6H2O,NaCl NaNO3·Na2SO4·2H2O,NaCl MgSO4·7H2O和NaCl MgSO4·(1~6)H2O.讨论了该相图在新疆硝酸盐矿开发利用过程中的应用.     

低温下Na //Cl-,SO42-,NO3-,H2O体系相平衡研究

采用等温溶解平衡法研究了四元体系Na+//Cl-,SO42-,NO-3-H2O在5、0、-5与-15℃下的相平衡关系。结果表明,4个温度下体系无复盐形成,平衡相图的构型基本一致;平衡相图均由3个结晶区(Na2SO4·10H2O、Na Cl和Na NO3)、3条单变量曲线(Na Cl-Na2SO4·10H2O、Na Cl-Na NO3、Na NO3-Na2SO4·10H2O)及1个共饱点(Na Cl-Na NO3-Na2SO4·10H2O)组成;4个温度下的平衡相图相比,随着温度的下降Na2SO4·10H2O结晶区不断扩大,Na Cl和Na NO3结晶区相对缩小;与该体系常温下的平衡相图相比,由于无复盐形成,低温下的相图大为简化。     

基于莫高窟成盐元素相关系探究壁画盐害作用机理

壁画盐害与壁画的成盐元素种类、盐分迁徙活动以及环境气象条件等密切相关.莫高窟壁画酥碱病变的可溶盐主要为NaCl和Na2SO4,盐的结晶是破坏力的重要来源.本文运用经典溶液化学的研究方法,界定了三元体系NaCl-Na2SO4-H2O于308K,298K,288K,278K,268K的相关系,以此为基础阐释了壁画盐害的发生和发展规律,计算得到了安全含盐量和环境条件的临界数值.研究表明:NaCl的饱和溶解度对温度敏感度不大,它的结晶析出更多的是伴随着水分的蒸发而发生;Na2SO4的饱和溶解度对温度表现较为敏感,它的结晶析出,除了因溶剂水分的蒸发而发生发展之外,还将因温度的降低而产生,他们各自在壁画盐害的发生发展过程中有一定的行为差异,其主导作用的交替点大致在wNa2SO4 /w NaCl=1:3～6左右,即当该体系中Na2SO4的质量比约达30%～15%时,Na2SO4将成为壁画盐害随洞窟温度变化而发生的主导诱因.三元体系NaCl-Na2SO4-H2O中NaCl和Na2SO4在5～35℃的介稳饱和溶解度的测定,取得了与相图相一致的结果.NaCl结晶物质地坚硬、粒度均匀,在壁画盐害表现形式上应以点状疱疹为主;Na2SO4结晶物主要以十水硫酸钠Na2SO4·10H2O的形式析出,质地疏松,易风化,易返潮,所导致的壁画酥碱病变有一定的反复性.Na2SO4的过饱和溶解度大,易富集,易浓缩,结晶区域较大,相应破坏面也较大,在壁画盐害的表现形式应以粉状酥碱为主,如壁画较大面积的空鼓、地仗层酥松等.     

298.16 K时Na+, Mg2+//Cl-, SO42-, NO3-, H2O体系中NaCl饱和区域相平衡

采用等温溶解平衡法研究了五元体系Na+, Mg2+//Cl-, SO42-, NO3-, H2O在298.16 K下氯化钠饱和平衡体系的溶解度, 获得了相应的投影干盐图、氯图和水图. 研究结果表明, 在298.16 K下氯化钠饱和时, 该五元体系投影干盐图由8个二盐共饱和的双变面、13条三盐共饱的单变线和6个四盐共饱的零变点构成, 存在两种复盐, 8个二盐共饱双变面分别对应于NaCl+NaNO3, NaCl+Na2SO4, NaCl+MgCl2·6H2O, NaCl+MgSO4·Na2SO4·4H2O, NaCl+Mg(NO3)2·6H2O, NaCl+NaNO3·Na2SO4·2H2O, NaCl+MgSO4·7H2O 和NaCl+MgSO4·(1—6)H2O. 讨论了该相图在新疆硝酸盐矿开发利用过程中的应用.     

硫酸镁亚型盐湖卤水高温蒸发析盐结晶规律（英文）

针对青海大浪滩盐湖区硫酸镁亚型盐田卤水进行了高温蒸发结晶规律的研究,结果表明该盐田卤水在102~122℃高温蒸发时析盐顺序为:MgSO4·H2O、NaCl、MgSO4·6H2O、KCl·MgCl2·6H2O和其他混盐.通过对不同温度下的液相组分分析和固相X射线衍射分析表明,利用高温蒸发开采此种卤水时,最适宜的蒸发温度应控制在117℃左右.此时,该卤水组成中SO2-4的质量分数低于2%,同时K+还未析出,可以简化为Na+,K+,Mg2+//Cl-—H2O四元体系,以便达到开采氯化钾的工艺需求,为该盐湖卤水的综合开发利用提供理论参考.     

高时空分辨率研究海盐液滴快速风化过程

以高速摄像仪与显微拉曼光谱联用研究聚四氟(疏水)乙烯基底和石英(亲水)基底上的单个海水液滴的快速风化过程.海水液滴风化的形貌图像达到毫秒时间分辨率和微米空间分辨率.通入干氮气后海水液滴在石英基底上发生快速风化过程,首先析出Na2Ca5(SO4)6·3H2O和Na2xCa8-x(SO4)6·3H2O(0＜x＜1)晶体,然后析出NaCI晶体,最后析出KMgCl3·6H2O晶体.我们发现在快速降低湿度的过程中析出钙钠复盐,在缓慢降低湿度的过程中析出CaSO4·2H2O,并已经确定各种结晶产物的位置以及Na2Ca5(SO4)6·3H2O和CaSO4· 2H2O两种晶体的生长速率,并在聚四氟乙烯基底上观察到中空结构的海盐颗粒.     

一种超支化疏水缔合聚合物的制备与性能评价

首先制备了疏水单体2-丙烯酰胺基十四烷磺酸,在此基础上又以改性Si O2功能单体为反应核制备了超支化疏水缔合聚合物(HBPAM),结构经红外光谱(FTIR)和核磁共振氢谱(1H NMR)表征证实。HBPAM在低浓度时主要是分子内缔合,表观黏度低,随着浓度的增加,分子内缔合逐渐变为分子间缔合,又因其独特的三维立体网状结构,溶液黏度显著增加。与梳形KYPAM相比,HBPAM在耐温抗盐及抗剪切方面有较高的优势:升温到85℃时黏度保留率为62.2%;100000mg·L-1Na Cl、150000 mg·L-1Na Cl、500 mg·L-1Mg Cl2、1000 mg·L-1Mg Cl2、500 mg·L-1Ca Cl2、1000 mg·L-1Ca Cl2时的黏度保留率分别为233.0%、132.9%、64.4%、26.1%、66.2%、15.7%;3400rpm/min剪切30s后HBPAM的黏度保留率为69.8%,比KYPAM高10.9%。在60℃烘箱中的30d老化实验证明,HBPAM比KYPAM有明显抗老化能力,尤其是在高矿化度条件下优势更明显。     

Crystallization and Phase Stability of CaSO<Subscript>4</Subscript> and CaSO<Subscript>4</Subscript> – Based Salts

Summary.  Calcium sulfate occurs in nature in form of three different minerals distinguished by the degree of hydration: gypsum (CaSO₄·2H₂O), hemihydrate (CaSO₄·0.5H₂O) and anhydrite (CaSO₄). On the one hand the conversion of these phases into each other takes place in nature and on the other hand it represents the basis of gypsum-based building materials. The present paper reviews available phase diagram and crystallization kinetics information on the formation of calcium sulfate phases, including CaSO₄-based double salts and solid solutions. Uncertainties in the solubility diagram CaSO₄–H₂O due to slow crystallization kinetics particularly of anhydrite cause uncertainties in the stable branch of crystallization. Despite several attempts to fix the transition temperatures of gypsum–anhydrite and gypsum–hemihydrate by especially designed experiments or thermodynamic data analysis, they still vary within a range from 42–60°C and 80–110°C. Electrolyte solutions decrease the transition temperatures in dependence on water activity. Dry or wet dehydration of gypsum yields hemihydrates (α-, β-) with different thermal and re-hydration behaviour, the reason of which is still unclear. However, crystal morphology has a strong influence. Gypsum forms solid solutions by incorporating the ions HPO₄ ²⁻, HAsO₄ ²⁻, SeO₄ ²⁻, CrO₄ ²⁻, as well as ion combinations Na⁺(H₂PO₄)⁻ and Ln³⁺(PO₄)³⁻. The channel structure of calcium sulfate hemihydrate allows for more flexible ion substitutions. Its ion substituted phases and certain double salts of calcium sulfate seem to play an important role as intermediates in the conversion kinetics of gypsum into anhydrite or other anhydrous double salts in aqueous solutions. The same is true for the opposite process of anhydrite hydration to gypsum. Knowledge about stability ranges (temperature, composition) of double salts with alkaline and alkaline earth sulfates (esp. Na₂SO₄, K₂SO₄, MgSO₄, SrSO₄) under anhydrous and aqueous conditions is still very incomplete, despite some progress made for the systems Na₂SO₄–CaSO₄ and K₂SO₄–CaSO₄–H₂O. Corresponding author. E-mail: daniela.freyer@chemie.tu-freiberg.de Received December 17, 2002; accepted January 10, 2003 Published online April 3, 2003     

Polyhalite and its analogous triple salts

Polyhalite (K₂SO₄ · MgSO₄ · 2CaSO₄ · 2H₂O) and analogue triple salts, where Mg²⁺ is substituted by Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺, have been synthesized. The salts were characterized by thermal analysis, Raman spectroscopy and X-ray powder diffraction. Diffraction patterns and Raman spectra resemble those of natural polyhalite, except K₂SO₄ · CuSO₄ · 2CaSO₄ · 2H₂O. The latter corresponds to the mineral leightonite, which is structurally different.     

Nature of influence exerted by Na<Subscript>2</Subscript>SiF<Subscript>6</Subscript> on REE recovery from orthophosphoric acid solution in the course of CaSO<Subscript>4</Subscript>·0.5H<Subscript>2</Subscript>O crystallization

Chemical and X-ray phase analyses were used to study the influence exerted by Na₂SiF₆ on the isomorphic inclusion of cerium into the structure of CaSO₄?0.5H₂O precipitates formed from solutions of phosphoric acid hemihydrate (38 wt % P₂O₅). The poorly soluble suspensions of CaSO₄?0.5H₂O precipitates can serve as adsorbents for cerium compounds, with CaSO₄?0.5H₂O–NaCe(SO₄)₂?H₂O and CaSO₄?0.5H₂O–CePO₄?0.5H₂O solid solutions formed. The introduction of Na₂SiF₆ makes the sorption properties CaSO4?0.5H2O several times better because the Na₂SiF₆ phase is a source of sodium cations and creates the necessary Na: Ce ratio of 1: 1 for extracting cerium from the liquid phase into a precipitate in the form of a CaSO₄?0.5H₂O–[NaCe(SO₄)₂?H₂O + CePO₄?0.5H₂O] solid solution. Under the industrial conditions in which extraction phosphoric acid is manufactured, a similar isomorphous capture of rare-earth elements of the cerium group (La–Sm) may occur in joint precipitation of CaSO₄?0.5H₂O and Na₂SiF₆.     

Polyhalite and its analogous triple salts

Polyhalite (K₂SO₄ · MgSO₄ · 2CaSO₄ · 2H₂O) and analogue triple salts, where Mg²⁺ is substituted by Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺, have been synthesized. The salts were characterized by thermal analysis, Raman spectroscopy and X-ray powder diffraction. Diffraction patterns and Raman spectra resemble those of natural polyhalite, except K₂SO₄ · CuSO₄ · 2CaSO₄ · 2H₂O. The latter corresponds to the mineral leightonite, which is structurally different. For polyhalite analogues the cell parameters of the triclinic unit cell have been determined from the powder diffraction patterns. The length of the unit cell vectors varies regularly with the ionic radius of the substituted ion M ²⁺ and is explained by changes in the extension of the coordination octahedron of M ²⁺. Thereby increasing distances of the coordinated water molecules at M ²⁺ parallel with decreasing dehydration temperatures of the corresponding polyhalite. Correspondence: Daniela Freyer, Institut für Anorganische Chemie, TU Bergakademie Freiberg, 09599 Freiberg, Germany.     

Zn4Si2O7(OH)2H2O盐修饰的纳米Ru催化剂催化苯选择加氢制环己烯

利用沉淀法制备了纳米Ru催化剂,在ZnSO₄存在下考察了Na₂SiO₃·9H₂O和二乙醇胺作反应修饰剂对Ru催化剂催化苯选择加氢制环己烯性能的影响,并用X-射线衍射(XRD)、X-射线荧光光谱(XRF)和透射电镜-能量散射谱(TEM-EDS)等物理化学手段对加氢前后Ru催化剂进行了表征。结果表明,在水溶液中Na₂SiO₃与ZnSO₄可以反应生成Zn₄Si₂O₇(OH)₂H₂O盐、H₂SO₄和Na₂SO₄,化学吸附在Ru催化剂表面上的Zn₄Si₂O₇(OH)₂H₂O盐起着提高Ru催化剂环己烯选择性的关键作用。Na₂SiO₃·9H₂O量的增加,生成的Zn₄Si₂O₇(OH)₂H₂O盐逐渐增加,Ru催化剂的活性降低,环己烯选择性逐渐升高。向反应体系中加入二乙醇胺,它可以中和Na₂SiO₃与ZnSO₄反应生成的硫酸,使化学平衡向生成更多的Zn₄Si₂O₇(OH)₂H₂O盐的方向移动,导致Ru催化剂环己烯选择性增加。当Ru催化剂与ZnSO₄·7H₂O、Na₂SiO₃·9H₂O和二乙醇胺、分散剂ZrO₂的质量比为1.0:24.6:0.4:0.2:5.0时,2 g Ru催化剂上苯转化73%时环己烯选择性和收率分别为75%和55%,而且该催化剂体系具有良好的重复使用性和稳定性。     

Zn4Si2O7(OH)2H2O盐修饰的纳米Ru催化剂催化苯选择加氢制环己烯

利用沉淀法制备了纳米Ru催化剂, 在ZnSO₄存在下考察了Na₂SiO₃·9H₂O和二乙醇胺作反应修饰剂对Ru催化剂催化苯选择加氢制环己烯性能的影响, 并用X-射线衍射(XRD)、X-射线荧光光谱(XRF)和透射电镜-能量散射谱(TEM-EDS)等物理化学手段对加氢前后Ru催化剂进行了表征。结果表明, 在水溶液中Na₂SiO₃与ZnSO₄可以反应生成Zn₄Si₂O₇(OH)₂H₂O盐、H₂SO₄和Na₂SO₄, 化学吸附在Ru催化剂表面上的Zn₄Si₂O₇(OH)₂H₂O盐起着提高Ru催化剂环己烯选择性的关键作用。Na₂SiO₃·9H₂O量的增加, 生成的Zn₄Si₂O₇(OH)₂H₂O盐逐渐增加, Ru催化剂的活性降低, 环己烯选择性逐渐升高。向反应体系中加入二乙醇胺, 它可以中和Na₂SiO₃与ZnSO₄反应生成的硫酸, 使化学平衡向生成更多的Zn₄Si₂O₇(OH)₂H₂O盐的方向移动, 导致Ru催化剂环己烯选择性增加。当Ru催化剂与ZnSO₄·7H₂O、Na₂SiO₃·9H₂O和二乙醇胺、分散剂ZrO₂的质量比为1.0:24.6:0.4:0.2:5.0时, 2 g Ru催化剂上苯转化73%时环己烯选择性和收率分别为75%和55%, 而且该催化剂体系具有良好的重复使用性和稳定性。     

Solid‐Liquid Equilibria in the Quinary Na+, K+//Cl−, SO2−4, B4O2−7‐H2O System at 298 K

The solid‐liquid equilibria in the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K had been studied experimentally using the method of isothermal solution saturation. Solubilities and densities of the solution of the quinary system were measured experimentally. Based on the experimental data, the dry‐salt phase diagram and water content diagram of the quinary system were constructed, respectively. In the equilibrium diagram of the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K, there are five invariant points F1, F2, F3, F4 and F5; eleven univariant curves E1F1, E2F2, E3F3, E4F5, E5F2, E6F4, E7F5, F1F4, F2F4 F1F3 and F3F5, and seven fields of crystallization saturated with Na₂B₄O₇ corresponding to Na₂SO₄, Na₂SO₄·10H₂O, Na₂SO₄·3K₂SO₄ (Gla), K₂SO₄, K₂B₄O₇·4H₂O, NaCl and KCl. The experimental results show that Na₂SO₄·3K₂SO₄ (Gla), K₂SO₄ and K₂B₄O₇·4H₂O have bigger crystallization fields than other salts in the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K.     

Solubility study of sodium, potassium and calcium sulfates and chlorides, in ammonia

Solubility of sodium, potassium and calcium sulfates and chlorides in 28% ammonia solution was determined through monitoring conductivity measurements and kinetics of solids dissolution as a function of temperature and stirring time. The major findings of the present study show that Na₂SO₄ and K₂SO₄ solutions conductivity follow straight linear segments with different slopes. However, in case of NaCl, KC1, CaCl₂ and CaSO₄ · 2H₂O, conductivity curves were continuous, monotonous and reach constants maximum values. The hypothesis of complex formation or dissolution via intermediaries such as NaNH₄SO₄ and KNH₄SO₄ salts seams to be true, through X-ray diffraction study of resulting deposits. Furthermore, the dissolution rates at 25°C of potassium and calcium chlorides in ammonia solution are higher than that reported in the literature for water. In fact, ammonia significantly reduces the solubility of K₂SO₄; conversely, a slight increase in this parameter was observed for CaSO₄.     

Darstellung und Eigenschaften von Na2CuII (SO4)2 · 6 H2O

Preparation and Properties of Na₂Cu^II (SO₄)₂ · 6 H₂O The preparation of the complex compound of Na₂Cu(SO₄)₂ · 6 H₂O is described. Its structure and properties were investigated using spectral methods (u.v.-vis., i.r., n.m.r.), by means of X-ray powder diffraction, and by thermal methods. On the basis of experimental results it is suggested that another member of the Tutton salts series has been prepared, appearring isostructural with them and showing the less distorted coordination polyhedron of [Cu(H₂O)₆]²⁺ from them. On its dehydration oxygen atoms from the sulphate groups enter the coordination sphere of Cu^II and the symmetry of SO₄^2? becomes lower. The experimental results indicate that Na₂Cu(SO₄)₂ · 6 H₂O as also Na₂Cu(SO₄)₂ as likewise Na₂Cu(SO₄)₂ · 2 H₂O are monoclinic.     

Physicochemical Analysis of the System Zr(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>–Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>–H<Subscript>2</Subscript>SO<Subscript>4</Subscript>–H<Subscript>2</Subscript>O at 25°С

The solubility in the quaternary water–salt system Zr(SO₄)₂ · 4Н₂О–Na₂SO₄–H₂SO₄–H₂O at 25°C was studied. It was found that, in the system, there is crystallization of not only Na₂SO₄ and Zr(SO₄)₄ · 4H₂O, but also sodium sulfate zirconates Na₂Zr(SO₄)₂(OH)₂ · 0.3H₂O, Na₄Zr(SO₄)₄ · 3H₂O, and Na₂Zr(SO₄)₂ · 3H₂O and two new compounds, S₁ and S₂, which are presumably Na₂ZrO(SO₄)₂ · 2H₂O and Na₂Zr₂O₂(SO₄)₃ · 6H₂O.