玄武岩类形成的大地构造环境Ta、Hf、Th、La、Zr、Nb比值对比判别

玄武质岩浆见于板块构造演化的全过程和各个重要阶段,是所有火成岩中最主要的构造地球化学指示剂,因此,玄武岩类相关元素图解和比值成为研究火成岩成岩作用和形成构造环境判别的首选对象。Ta、Hf、Th、La、Zr、Nb都是高场强元素和较强不相容元素,由于地球化学性质的相似性和在玄武岩类成岩过程中的规律性变化,所以它们是玄武岩类成因研究和构造环境判别图解中使用频率最高的元素,而且两两元素含量之间的比值能较好地区分其形成时的构造环境。在前人发明的玄武岩类Th/Hf-Ta/Hf、Th/Zr-Nb/Zr及La/Zr-Nb/Zr双对数判别图解基础上,运用这6个元素两两组对的Ta/Hf、Th/Ta、Th/Hf、Nb/Zr、Th/Nb、La/Nb值,建立比值判别表,极好地区分了几乎最常见的各种构造环境中有关的玄武岩类。该比值判别表是对双对数判别图解的极好补充。

高熵(Zr,Hf,Nb,Ta)C微米长方体的制备、吸波性能和抗氧化性研究

针对高熵碳化物制备困难,本文采用ZrC、HfC、NbC和TaC粉为原料,Ni粉为熔剂,通过低温无压烧结工艺成功制备出三种不同成分的高熵(Zr, Hf, Nb, Ta)C粉体。结果表明,三种粉体均为微米长方体,且暴露(100)晶面。(Zr_(1/4)Hf_(1/4)Nb_(1/4)Ta_(1/4))C微米长方体因具有高介电常数而展现出优异的吸波性能,在厚度为3.5 mm、频率为6.16 GHz时,最低反射损耗值可达-48.86 dB。高熵(Zr, Hf, Nb, Ta)C微米长方体在800~1 200℃下展示出优异的抗氧化性,且氧化产物均由正交相(Nb_(x)Ta_(1-x))_(2)O_(5)固溶体、单斜相(Zr_(x)Hf_(1-x))O_(2)固溶体和正交相HfO_(2)所组成,与氧化温度和过渡金属的物质的量比无关。Zr、Hf、Nb和Ta的协同作用导致其氧化机制与单组元碳化物截然不同,Hf的存在抑制Nb_(2)O_(5)由正交晶系向单斜晶系转变,还会促使ZrO_(2)在800℃时由四方晶系转变为单斜晶系。此外,Nb和Ta的存在促使HfO_(2)在常压下由单斜晶系转变为四方晶系。

峨眉山大火成岩省赋Nb-Ta-Zr矿化正长岩脉的形成时代和锆石Hf同位素组成

攀西地区广泛发育Nb-Ta-Zr矿正长岩脉,它们在空间上与峨眉山大火成岩省的玄武岩、辉长岩及长英质岩体(正长岩和花岗岩)共生,但是否有成因联系并不清楚。本文对攀西地区炉库和白草两个Nb-Ta-Zr矿区中的正长岩体、无矿及含矿正长岩脉进行了锆石LA-ICPMS法U-Pb定年和Lu-Hf同位素研究。研究表明,炉库矿区正长岩体和无矿正长岩脉锆石UPb年龄为255.6±2.0Ma和255.6±1.5Ma,含矿正长岩脉为256.7±4.4Ma;白草矿区正长岩体和含矿正长岩脉形成时间为257.9±2.3Ma和257.8±1.3Ma。这些年龄结果均显示攀西地区Nb-Ta-Zr矿化的形成时代与正长岩体一致,说明Nb-Ta-Zr矿化的形成与峨眉山大火成岩省紧密相关,为地幔柱成矿系统的一部分。两个矿区含矿正长岩脉的锆石εHf(t)值分别为+0.1^+9.5(多数集中于+2^+6,炉库矿区)和-0.2^+7.7(白草矿区),与正长岩体相似(炉库矿区为+1.0^+6.6,白草矿区为+2.1^+6.2),说明含矿岩脉与正长岩体有紧密成因联系。结合锆石年龄和Hf同位素研究初步认为,正长岩体和正长岩脉是峨眉山地幔柱岩浆底侵到下地壳底部的基性岩再次部分熔融的结果。

高级变质岩中Zr、Hf、Nb、Ta的ICP-MS准确分析

采用高压密闭溶样ICP -MS研究了片麻岩、榴辉岩等高级变质岩中Nb、Ta、Zr、Hf准确分析方法 .实验表明 :在温度为 190℃时 ,溶样时间大于 36h ,Nb、Ta、Zr、Hf可完全溶解 ,而获得准确的分析结果 .但Nb、Ta在稀硝酸介质中的不稳定性会导致分析结果的误差 ,采用 0 .1%HF介质的“F-基体”匹配 ,可保持Nb、Ta长时间的稳定性 .所建立的高压密闭溶样ICP-MS分析方法用于苏鲁—大别地区片麻岩、榴辉岩等高级变质岩的分析 ,经与XRF及碱熔融ICP -MS方法对比 ,分析结果具有良好的一致性 .

佛冈高分异I型花岗岩的成因:来自Nb-Ta-Zr-Hf等元素的制约

华南南岭地区发育有大面积的与钨锡成矿相关的侏罗纪花岗岩,然而其中有些花岗岩的成因类型却难以确定。本文以佛冈岩体为例,结合前人已发表数据,对佛冈花岗岩体中Nb、Ta、Zr和Hf等元素的迁移特征及其原理进行探讨,并对佛冈花岗岩的成因类型进行了厘定。随着分异程度增加,佛冈花岗岩Nb和Ta含量增加,Nb/Ta（3.6～15.3）和Zr/Hf（17.3～38.9）比值降低并发生分异。随着Zr含量的降低,佛冈花岗岩的Zr/Hf比值降低,这一特征表明锆石的分离结晶作用使得佛冈花岗岩的Zr/Hf比值分异。Nb/Ta比值分异可能与角闪石和黑云母的分离结晶作用有关。随着Nb/Ta比值降低,Y/Ho比值增加,这一特征表明佛冈花岗岩Nb/Ta比值的分异也和岩浆演化后期的流体有关。佛冈花岗岩不含原生的富铝矿物,为准铝质到弱过铝质岩石。随着分异程度增加,佛冈花岗岩P2O5含量降低,表明它不是S型花岗岩。随着Y/Ho比值增加和Nb/Ta和Zr/Hf比值降低,佛岗花岗岩Ga/Al和Fe OT/Mg O比值增加,从典型I型花岗岩特征演化到类似A型花岗岩的地球化学特征。因此,我们认为佛冈花岗岩不是A型花岗岩而是高分异的I型花岗岩。区域上与成矿相关的流体和花岗质岩浆的相互作用和分离结晶作用,使得华南南岭地区的花岗岩地球化学特征复杂,所以其成因类型也变的难以确定。

Nb-and Ta-doped(Hf,Zr,Ti)C multicomponent carbides with enhanced oxidation resistance at 2500℃

Enhancing oxidation resistance of multicomponent carbides above 2000℃is critical for their thermal protection applications.For this purpose,novel Nb-and Ta-doped(Hf,Zr,Ti)C multicomponent carbides were designed to improve their oxidation resistance at 2500℃.The results demonstrated that Nb and Ta doping reduced the oxidation rate constant by 16.67%and 25.17%,respectively,thereby significantly improving the oxidation resistance of(Hf,Zr,Ti)C.This enhancement was attributed to the changes in oxycarbide composition and distribution within the oxide layer by adding Nb and Ta.Owing to the different oxidation tendencies of the constituent elements,a distinctive structure was formed in which(Hf,Zr)O_(2)served as a skeleton,and various oxycarbides were dispersed throughout the oxide layer.The doped Nb and Ta were retained within oxycarbides,retarding the diffusion of oxygen into the lattice.More importantly,the addition of Nb and Ta reduced the size of oxycarbides,decreasing both size and quantity of the pores in the oxide layer and facilitating the formation of a more effective oxygen barrier.

High porosity and low thermal conductivity high entropy(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2C

Porous ultra-high temperature ceramics(UHTCs)are promising for ultrahigh-temperature thermal insulation applications.However,the main limitations for their applications are the high thermal conductivity and densification of porous structure at high temperatures.In order to overcome these obstacles,herein,porous high entropy(Zr(0.2)Hf(0.2)Ti(0.2)Nb(0.2)Ta(0.2))C was prepared by a simple method combing in-situ reaction and partial sintering.Porous high entropy(Zr(0.2)Hf(0.2)Ti(0.2)Nb(0.2)Ta(0.2))C possesses homogeneous microstructure with grain size in the range of 100–500 nm and pore size in the range of 0.2–1μm,which exhibits high porosity of 80.99%,high compressive strength of 3.45 MPa,low room temperature thermal conductivity of 0.39 W·m^-1K^-1,low thermal diffusivity of 0.74 mm^2·s^-1and good high temperature stability.The combination of these properties renders porous high entropy(Zr(0.2)Hf(0.2)Ti(0.2)Nb(0.2)Ta(0.2))Cpromising as light-weight ultrahigh temperature thermal insulation materials.

On the Enigma of Nb-Ta and Zr-Hf Fractionation——A Critical Review

Elemental ratios Zr/Hf and Nb/Ta are expected to be constant and of chondritic value （-36.30 and -17.57, respectively） in mantle and mantle-derived rocks. Studies in recent years have shown, however, that these two ratios do vary in some of these rocks. For example, MORB-like seamount lavas from flanks of the East Pacific Rise （EPR） show a correlated Zr/Hf （-25-50） and Nb/Ta （-9-18） variation. These two ratios are also correlated with ratios of more incompatible over less incompatible elements （e.g., La/Sm, Rb/Cs, Th/U, Nb/U, Sm/Yb） and with radiogenic isotope ratios （e.g., 87 Sr/86Sr, 143Nd/144Nd）. Furthermore, abyssal peridotites, which are melting residues for MORB, also show a huge correlated variation between Zr/Hf （-2.5-335） and Nb/Ta （-1-170）. All these observations plus a correlated variation between Zr/Hf （-22-48） and Nb/Ta （-10-23） in lunar rocks are consistent with the Zr-Hf and Nb-Ta fractionation being of magmatic origin. This contrasts with the common view that geochemical processes cannot readily fractionate them. As charges and ionic radii are the principal factors in the general theory of elemental fractionation, this theory cannot explain the fractionation of these two element pairs with the same charges （i.e., 5＋ for Nb and Ta, and 4＋ for Zr and Hf） and essentially the same ionic size （i.e., RNb/RTa=1.000, Rzr/RHf=1.006 to -1.026 for coordination numbers of 6, 7, 8 and 12）. We explore the possibilities of other factors and processes （e.g., mass-dependent fractionation during magmatism） that may cause the observed Nb-Ta and Zr-Hf fractionation. We emphasize that understanding the correlated Nb-Ta and Zr-Hf fractionation ＂known＂ to take place during magmatism is fundamental for improved understanding of elemental fractionations through other earth processes in various tectonic environments, including the origin and evolution of continental crust, which has a characteristic subchondritic Nb/Ta value of -11-12.

Porous high entropy(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2: A novel strategy towards making ultrahigh temperature ceramics thermal insulating

Transition metal diborides based ultrahigh temperature ceramics(UHTCs) are characterized by high melting point, high strength and hardness, and high electrical and thermal conductivity. The high thermal conductivity arises from both electronic and phonon contributions. Thus electronic and phonon contributions must be controlled simultaneously in reducing the thermal conductivity of transition metal diborides. In high entropy(HE) materials, both electrons and phonons are scattered such that the thermal conductivity can significantly be reduced, which opens a new window to design novel insulating materials. Inspired by the high entropy effect, porous HE(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2 is designed in this work as a new thermal insulting ultrahigh temperature material and is synthesized by an in-situ thermal borocarbon reduction/partial sintering process. The porous HE(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2 possesses high porosity of 75.67%, pore size of 0.3–1.2 μm, homogeneous microstructure with small grain size of 400–800 nm, which results in low room temperature thermal diffusivity and thermal conductivity of 0.74 mm2 s^-1 and 0.51 W m^-1K^-1, respectively. In addition, it exhibits high compressive strength of3.93 MPa. The combination of these properties indicates that exploring porous high entropy ceramics such as porous HE(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2 is a novel strategy in making UHTCs thermal insulating.

Cr-assisted low-temperature densification of(Ti,Zr,Nb,Ta,Mo)C high-entropy carbides with ultrafine grain and enhanced hardness

While the use of low-melting-point metals as sintering aids for high-entropy carbide(HEC)ceramics has been well established,their existence can compromise hardness due to residual metallic inclusions.This study demonstrates an innovative strategy to meet this challenge,where(Ti,Zr,Nb,Ta,Mo)C high-entropy carbide ceramics with ultrafine grains and enhanced hardness are obtained through chromium(Cr)-metal-assisted spark plasma sintering(SPS)at a temperature as low as 1600℃.The results show that the addition of 5 vol%Cr promotes the formation of highly densified single HEC phase ceramics with a high relative density(98.4%)and an ultrafine-grained microstructure(0.17μm).This low-temperature densification mechanism can be attributed to Cr’s solid-solution effect within the matrix and the increased carbon vacancies generated during sintering.The grain size of the(Ti,Zr,Nb,Ta,Mo)C ceramics with 5 vol%Cr metal addition is significantly smaller than that of Cr-free(Ti,Zr,Nb,Ta,Mo)C ceramics sintered at 2000℃(3.03μm)or via traditional low-temperature liquid-phase sintering(1.3–1.5μm).Importantly,the addition of 5 vol%Cr substantially increased the hardness of the ceramics,with a remarkable increase from 23.57 to 28.16 GPa compared to that of the pure(Ti,Zr,Nb,Ta,Mo)C ceramics,owing to the fine-grain strengthening and solid-solution strengthening mechanisms.This work highlights the uniqueness of Cr metal as a sintering aid in achieving densification and hardness improvements in(Ti,Zr,Nb,Ta,Mo)C ceramics,offering a promising strategy for improving the properties of HEC materials for further development in the near future.

Single-source precursor derived high-entropy metal–carbide nanowires:Microstructure and growth evolution

In recent years,high-entropy metal carbides(HECs)have attracted significant attention due to their exceptional physical and chemical properties.The combination of excellent performance exhibited by bulk HEC ceramics and distinctive geometric characteristics has paved the way for the emergence of one-dimensional(1D)HECs as novel materials with unique development potential.Herein,we successfully fabricated novel(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C nanowires derived via Fe-assisted single-sourced precursor pyrolysis.Prior to the synthesis of the nanowires,the composition and microstructure of(Ti,Zr,Hf,Nb,Ta)-containing precursor(PHECs)were analyzed,and divinylbenzene(DVB)was used to accelerate the conversion process of the precursor and contribute to the formation of HECs,which also provided a partial carbon source for the nanowire growth.Additionally,multi-branched,single-branched,and single-branched bending nanowires were synthesized by adjusting the ratio of PHECs to DVB.The obtained single-branched(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C nanowires possessed smooth surfaces with an average diameter of 130–150 nm and a length of several tens of micrometers,which were a single-crystal structure and typically grew along the[11¯1]direction.Also,the growth of the(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C nanowires was in agreement with top-type vapor–liquid–solid mechanism.This work not only successfully achieved the fabrication of HEC nanowires by a catalyst-assisted polymer pyrolysis,but also provided a comprehensive analysis of the factors affecting their yield and morphology,highlighting the potential application of these attractive nano-materials.

海水中某些稀有金属的分离预富集和ICP光谱法测定研究

本文提出了以聚二硫代氨基甲酸盐螯合树脂分离预富集－ＩＣＰ－ＡＥＳ测定海水中稀有金属Ｕ，Ｎｂ，Ｔａ，Ｚｒ和Ｈｆ的新方法。对上述元素与螯合树脂在不同ｐＨ下的静态交换行为进行了研究。考察了溶液酸度，流速及基体元素对分离富集效果的影响，比较了吸附在树脂上的待测元素的解脱方法。在优化的实验条件下，方法的相对检出限为０．０２～０．１７ｎｇ／ｍＬ，应用于海水试样分析时，其回收率在８１％～９４％之间。

电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中的铌钽锆铪

建立电感耦合等离子体质谱法（ICP-MS）测定水系沉积物中铌、钽、锆、铪四种元素的分析方法。将样品与氢氧化钠、过氧化钠混合物放入高温炉中,熔融分解完全,用热水提取,过滤后弃去滤液,将滤纸及沉淀用酒石酸-盐酸溶液溶解,稀释至刻度测定。方法检出限（3s）为：LD（Nb）=0.08μg/g,LD（Ta）=0.04μg/g,LD（Zr）=0.5μg/g,LD（Hf）=0.04μg/g,精密度（RSD%,n=6）为：0.84%~4.21%。该测定方法具有灵敏度高、精密度好、分析速度快、线性范围宽、操作性强等优势。采用该方法对国家一级标准物质进行测定表明,其结果与标准值吻合。此方法已在实际地质调查样品分析中得到应用。

敞开酸溶和偏硼酸锂碱熔ICP-MS法测定多金属矿中的稀土元素及铌钽锆铪

用电感耦合等离子体质谱法(ICP-MS)测定地质样品中的稀土及难熔元素,混合酸敞开酸溶法和碱熔融法是两种主要的溶样方法。但地质样品组分复杂,元素之间存在相互共生的现象,对于特殊元素、特殊样品用传统酸溶法会造成部分元素消解不完全,使测定结果不准确;而碱熔法的操作过程繁琐,且溶液盐度高,易产生基体干扰和堵塞仪器进样系统。本文改进了传统四酸和五酸体系,采用氢氟酸-硝酸-硫酸敞开酸溶体系,用国家一级标准物质制作标准曲线测定15种稀土元素,方法准确度(ΔlgC)为0.001~0.027。同时改进了偏硼酸锂碱熔法,样品用偏硼酸锂碱熔提取,加入氢氧化钠调节溶液至碱性条件,所测元素与偏硼酸锂共沉淀后过滤分离熔剂,再用硝酸复溶测定15种稀土元素及铌钽锆铪。两种溶样方法的测定值与认定值的相对误差为1.09%~9.30%。将混合酸敞开酸溶法测定稀土元素、偏硼酸锂碱熔法测定铌钽锆铪的结果与其他实验室密闭酸溶法相比,两组数据的相对偏差为0.13%~15.32%。本实验表明,混合酸敞开酸溶法适用于测定地质样品中的稀土元素,偏硼酸锂碱熔法不仅适用于测定地质样品中的稀土元素及铌钽锆铪,也适用于测定如古老高压变质岩石及铝含量高的样品中的铌钽锆铪。

ICP-AES法测定高温合金中铌、钽、锆、铪──溶样及光谱干扰的进一步探讨

本文在原工作的基础上，继续探讨ICP－AES法测定高温合金中Nb、Ta、Zr和Hf的落样与光谱干扰问题，通过试验研究表明，上述问题的解决在合金样品分析中具有实际意义．

ICP－AES法测定高温合金中铌、钽、锆、铪

本文研究了高温合金中Ｎｂ、Ｔａ、Ｚｒ和Ｈｆ的分析方法，同时探讨了ＩＣＰ－原子发射光谱法中的某些影响因素及其校正。通过精密度与准确度试验，表明该分析方法准确、可靠，并且用于合金样品分析取得了满意的效果。

等离子体质谱法测定岩石中的锆、铪、铌、钽

本文建立了用HF、HNO3 在高压釜内溶解样品 ,准确测定花岗岩样品中Nb、Ta、Zr、Hf的ICP MS分析方法。分析结果与推荐值的偏差在 5 %以内。该方法具有简单、准确、测定元素多的特点。本文还对高压釜酸溶和碱熔方法进行了对比实验。

塔里木盆地东南缘安南坝地区镁铁质麻粒岩的成因--来自地球化学及Sr-Nd-Pb同位素的制约

甘肃阿克塞县安南坝地区镁铁质麻粒岩呈脉状、透镜状赋存于新太古代米兰岩群和TTG片麻岩中。岩石主要由斜长石(Pl)+斜方辉石(Opx)+单斜辉石(Cpx)+角闪石(Amp)+磁铁矿(Mt)等组成。安南坝镁铁质麻粒岩中Ti、P、Nb、Ta、Th、Hf、Sr及REE等元素与Zr相关性较好,表明其在变质作用过程中保持基本稳定。地球化学数据显示其原岩属于拉斑玄武质岩系列,Si O_2、Ti O_2、Al_2O_3、P_2O_5含量相对较低,Ca O、Mg O含量相对较高。Mg~#值为41.52~43.09,低于原生玄武质岩石的Mg~#值,Fe_2O_3~T、Mg O、Ca O与Si O_2含量呈负相关性,指示原岩岩浆演化过程中可能发生了辉石、角闪石等镁铁质矿物的分异结晶作用。镁铁质麻粒岩∑REE较低,稀土元素配分模式为轻稀土元素弱富集、重稀土元素相对平坦的右倾型,Eu异常不明显(Eu/Eu~*=0.91~1.01)。岩石富集Rb、Ba、Sr等大离子亲石元素,亏损Nb、Ta、Zr、Ti等高场强元素,具有显生宙典型岛弧玄武质岩石的地球化学特征。Sr、Nd、Pb同位素组成显示镁铁质麻粒岩原岩源自富集地幔,并受到一定程度的地壳物质混染。构造环境分析表明安南坝镁铁质麻粒岩原岩形成于与俯冲有关的岛弧环境。在俯冲作用机制下,俯冲板片流体交代使地幔楔发生富集,形成富集地幔,随着(弧后)伸展作用的加强,进一步诱发富集地幔的部分熔融形成镁铁质岩浆,最终岩浆就位形成辉长岩或辉绿岩脉,后期在麻粒岩相变质作用条件下变质为镁铁质麻粒岩。

等离子体发射光谱法同时测定岩石中微量锆、铪、铌和钽等元素

本文介绍了一种快速离子交换分离—ICP-AES法同时测定岩石中微量锆、铪、铌和钽等元素的新方法。样品经碱熔、浸取、过滤,其沉淀连同滤纸放回原烧杯,加入H^+型阳离子交换树脂和少量酒石酸溶液。基体元素(Fe^(3+),Al^(3+),Ca^(2+),Mg^(2+)等)被树脂吸附,锆、铪、铌和钽与酒石酸形成稳定络合物存留在溶液中,经干过滤后,用ICP-AES方法直接测定。欲测元素的样品分析实际检出限分别为:Zr0.2ppm。Hf、Nb、Ta均为0.4ppm。实践证明,本方法不仅步骤简单,分析速度快,而且分析结果或靠,精密度和准确度良好。