锡铁山石晶体结构中Fe3+的两种亚晶位

对产于青海锡铁山铅锌矿氧化带中的锡铁山石进行了５７Ｆｅ穆斯堡尔谱的研究，在晶体结构分析的基础上进行了谱峰的重新解释，发现由于配位Ｃｌ－离子无序占位引起Ｆｅ３＋离子所占配位八面体的畸变，形成了Ｆｅ３＋的两种亚晶位，并根据结构数据指定了这两种亚晶位各自形成的四极双峰。     

Fe2+在零价铁还原去除NO3-中的作用效应

零价铁（Fe0） 被广泛用于地下水中硝酸盐原位与异位修复,但二价铁（Fe2+） 的存在对具有氧化膜的Fe0还原硝酸盐的作用效应仍有待研究。以100 目的未经酸化的颗粒状零价铁作为还原剂,采用室内批试验方法,研究了Fe2+在零价铁还原去除NO3-系统中的作用效应。实验结果表明,Fe2+可显著提高Fe0对于NO3-的去除速率与去除效率,且Fe2+浓度越高,去除速率与效率越高;由于未经酸化的Fe0具有氧化膜,反应初期的NO3-还原速率较慢。Fe2+将零价铁表面的Fe2O3氧化膜转化为Fe3O4,加速电子由Fe0向NO3-的转移,促进NO3-还原。此外,在反应系统中加入Fe3O4,可进一步提高Fe0对于硝酸盐的去除能力,若Fe2+不存在,仅添加Fe3O4,NO3-的去除效率没有提高。     

Crystal chemistry of Fe3+-bearing (Mg,Fe)SiO3 perovskite: a single-crystal X-ray diffraction study

Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO₃ perovskite more accurately, we synthesized single crystals of Mg_0.946(17)Fe_0.056(12)Si_0.997(16)O₃ perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe²⁺ and Fe³⁺) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O₃ perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.     

57Fe mössbauer study of synthetic Fe3+-melilites

Synthetic Fe³⁺-melilites containing NaCaFe³⁺-Si₂O₇-, Ca₂Fe³⁺AlSiO₇- or Sr₂Fe³⁺AlSiO₇-components have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe³⁺Si₂O₇-component consists of one doublet identified to belong to Fe³⁺ in T1 sites. The spectra of åkermanite and gehlenite containing Ca₂Fe³⁺ AlSiO₇- or Sr₂Fe³⁺ AlSiO₇-component consist of two doublets. The inner and outer doublets are identified to belong to Fe³⁺ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe³⁺ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe³⁺ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic.     

Fe3+纳米胶体颗粒的光吸收边蓝移与溶液中Al/Fe比的关系

合成了n（Al）／n（Fe）和碱化度不同的45个聚合氯化铝铁（PAFC）样品,进行了光谱分析,结果显示光吸收边蓝移或红移以及Fe（Ⅲ）羟基氧化物和Al-Fe共聚体纳米胶体颗粒大小分布与溶液的Al／Fe比和碱化度（B=[OH]／[Al＋Fe]）密切相关。电镜观察和电子衍射分析表明：Al（Ⅲ）的加入使Fe（Ⅲ）羟基氧化物和Al-Fe共聚体纳米胶体颗粒变小、有序度降低是造成PAFE光吸收边蓝移和保持胶体颗粒在亚稳定状态下存在的重要原因。当n（Al）／n（Fe）〉8：2后,PAFC溶液中Fe（Ⅲ）羟基氧化物和Al-Fe共聚体胶体主要以〈10m的纳米颗粒形态存在,对应的光谱能级提高到26000cm^-1以上,且各种曰值下Fe^3＋的光谱能级趋于一致。这表明,在大量Al（Ⅲ）存在条件下,PAFE中Fe3^＋的所处的化学环境相似。点能谱分析显示,n（Al）／n（Fe）=4：6的样品中颗粒物的化学计量比最接近AlOOH,FeOOH,溶液的稳定性最差。     

Determination of Fe3+ and Fe2+ concentrations in feldspar by optical absorption and EPR spectroscopy

Ferrous and ferric iron concentrations in feldspars with low total iron content (<0.32 wt% total Fe) were determined from optical and electron paramagnetic resonance (EPR) spectra to better than ±15 percent of the amount present. Optical spectra indicate that Fe²⁺ occupies two distorted M-sites in plagioclases of intermediate structural state. The linear dependence of the Fe²⁺/Fe total ratio on An content demonstrates that Fe²⁺ substitutes for Ca (not Na) so that the number of Ca-sites is a principal factor in iron partitioning in plagioclase. EPR powder spectra show that the number of sites for Fe³⁺ depends on structural state rather than on plagioclase chemistry. The observed linear correspondence of EPR double-integrated intensities with optical peak areas shows that all Fe³⁺ is tetrahedrally coordinated in both plagioclase and disordered potassium feldspar. Microcline perthites show, in addition to tetrahedral Fe³⁺, a signal due to axially coordinated ferric iron, which we associate with formation of hematite inclusions.     

Nikmelnikovite,Ca 12 Fe 2+ Fe $$_{3}^{{3 + }}$$ Al 3 (SiO 4 ) 6 (OH) 20 : A New Mineral from the Kovdor Massif (Kola Peninsula,Russia)

Doklady Earth Sciences - Nikmelnikovite, Ca12Fe2+Fe$$_{3}^{{3 + }}$$Al3(SiO4)6(OH)20, a new mineral from the Kovdor massif (Kola Peninsula, Russia), is described. It is the first trigonal...     

Synthesis of New Polytypic Modifications of Fe7C3 at 5.5 GPa

Doklady Earth Sciences - The results of experimental synthesis of carbide Fe7C3 at 5.5 GPa are presented. It is found that carbide Fe3C and several polytypes of carbide Fe7C3 are formed along with...     

Synthesis and stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10, and Fe3+⇋Al3+ substitutions at 15–28 kb

Deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀, thus far known from ten localities in glaucophane schist terranes, was synthesized at water pressures of 20–25 kb and temperatures of 550–600 °C under the of the Ni/NiO buffer. The X-ray powder diagram, lattice constants and infrared spectrum of the synthetic phase are closely similar to those of the natural mineral. A solid solution series extends from this ferri-deerite end member to some 20 mole % of a hypothetical alumino-deerite, Fe ₁₂ ²⁺ Al ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. The upper temperature breakdown of ferri-deerite to the assemblage ferrosilite +magnetite+quartz+water occurs at about 490 °C at 15 kb, and 610 °C at 25 kb fluid pressure for the of the Ni/NiO buffer. Extrapolation of these data to lower water pressures indicates that deerite can be a stable mineral only in very low-temperature, high-pressure environments.     

Ziminaite,Fe3+VO4, a new howardevansite-group mineral from the Bezymyannyi volcano,Kamchatka, Russia

Mineralogy and Petrology - The new mineral ziminaite, ideally Fe3+VO4, was found in fumarole sublimates at the Bezymyannyi volcano, Kamchatka, Russia. Ziminaite occurs as lamellar, tabular or...     

The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite

Summary Tetrahedrites with the composition between Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of⁵⁷Fe. Between Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ iron is predominantly ferric. Between Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ iron is predominantly ferrous and occupies the tetrahedral M1-sites.

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Zusammenfassung Die Rolle von Fe²⁺ und Fe³⁺ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von⁵⁷Fe untersucht. Zwischen Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ ist Eisen überwiegend dreiwertig. Zwischen Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₁Fe₂Sb₄S₁₃ ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.

     

Cordierite III: the site occupation and concentration of Fe3+

Cordierite has the ideal formula (Mg,Fe)₂Al₄Si₅O₁₈ ^.x(H₂O,CO₂), but it must contain some Fe³⁺ to account for its blue color and strong pleochroism. The site occupation and concentration of Fe³⁺ in two Mg-rich natural cordierites have been investigated by EPR and ⁵⁷Fe Mössbauer spectroscopy. In addition, powder IR spectroscopy, X-ray diffraction, and TEM examination were used to characterize the samples. Single-crystal and powder EPR spectra indicate that Fe³⁺ is located on T₁1 in natural cordierites and not in the channels. The amount in Mg-rich cordierites is very small with an upper limit set by Mössbauer spectroscopy giving less than 0.004 cations per formula unit (pfu). Fe³⁺ in cordierite can, therefore, be considered insignificant for most petrologic calculations. Heat-treating cordierite in air at 1,000?°C for 2?days causes an oxidation and/or loss of Fe²⁺ on T₁1, together with an expulsion of Na⁺ from the channels, whereas heating at the Fe–FeO buffer produces little Fe³⁺ in cordierite. Heating at 1,000?°C removes all class I H₂O, but small amounts of class II H₂O remain as shown by the IR measurements. No evidence for channel Fe²⁺ or Fe³⁺ in the heat-treated samples was found. The blue color in cordierite arises from a broad absorption band (E//b and weaker with E//a) around 18,000?cm^?1 originating from charge-transfer between Fe²⁺ in the octahedron and Fe³⁺ in the edge-shared T₁1 tetrahedron. It therefore appears that all natural cordierites contain some tetrahedral Fe³⁺. The brown color of samples heated in air may be due to the formation of very small amounts of submicroscopic magnetite and possibly hematite. These inclusions in cordierite can only be identified through TEM study.     

Die Kristallstruktur des Voltaits,K2Fe 5 2+ Fe 3 3+ Al[SO4]12·18H2O

Zusammenfassung Die Kristallstruktur von künstlichem Voltait, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂· ·18 H₂O, kubisch hexakisoktaedrisch,Fd3c–O _h ⁸,a ₀=27,254 ,Z-16, wurde mittels photographischer Röntgendaten bestimmt. Die Aufklärung der Struktur erfolgte mit Patterson- und Fouriermethoden unter Zuhilfenahme des multiplen isomorphen Ersatzes. Die Verfeinerung nach der Methode der kleinsten Quadrate ergab mit anisotropen Temperaturfaktoren für 726 beobachteteF _hkl R=0,033. Das Hauptmerkmal der Struktur ist ein 3dimensionales Gerüst aus [Fe³⁺O₆]-Oktaedern, [Fe ₅ ^6/2+ Fe ₁ ^6/3+ O₄(H₂O)₂]-Oktaedern und [K⁺O₁₂]-Polyedern, die durch SO₄-Tetraeder verknüpft werden. Hohlräume dieses Gerüstes werden von ungeordnet orientierten [Al(H₂O)₆]-Oktaedern eingenommen. Es wird gezeigt, daß Al als wesentlicher Bestandteil dieses Voltaits angesehen werden muß.

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The crystal structure of voltaite, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂·18H₂O

Summary The crystal structure of synthetic voltaite, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂· · 18 H₂O, cubic hexakis-octahedral, space groupFd3c–O _h ⁸,a ₀=27.254 ,Z=16, was determined from photographic X-ray data. The structure was solved by Patterson and Fourier-methods with the aid of multiple isomorphic substitution. Least squares refinement with anisotropic temperature factors resulted inR=0.033 for 726 observedF _hkl . The dominant structural feature is a continous framework composed of [Fe³⁺O₆]-octahedra, [Fe ₅ ^6/2+ Fe ₁ ^6/3+ O₄(H₂O)₂]-octahedra and [K⁺O₁₂]-polyhedra linked by SO₄-tetrahedra. The arrangement gives rise to cages occupied by disordered [Al(H₂O)₆]-octahedra. It is shown that Al must be considered to be a essential constituent of such voltaites.

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Mit 2 Abbildungen     

The P-T-fO 2 stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10

New equilibrium experiments have been performed in the 20–27 kbar range to determine the upper thermal stability limit of endmember deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. In this pressure range, the maximum thermal stability limit is represented by the oxygen-conserving reaction: deerite(De)=9 ferrosilite(Fs)+3 magnetite(Mag)+3 quartz(Qtz)+5 H₂O(W) (1). Under the oxygen fugacities of the Ni-NiO buffer the breakdown-reduction reaction: De=12 Fs+2 Mag+5 W+1/2 O₂ (10) takes place at lower temperatures (e.g. T=63° at 27 kbar). The experimental brackets can be fitted using thermodynamic data for ferrosilite, magnetite and quartz from Berman (1988) and the following 1 bar, 298 K data for deerite (per gfw): V^o=55.74 J.bar^-1, S^o=1670 J.K^-1, H _f ^o =-18334 kJ, =2.5x10^-5K^-1, =-0.18x10^-5 bar^-1. Using these data in conjunction with literature data on coesite, grunerite, minnesotaite, and greenalite, the P-T stability field of endmember deerite has been calculated for P _s=P _{H 2}O. This field is limited by 6 univariant oxygenconserving dehydration curves, from which three have positive dP/dT slopes, the other three negative slopes. The lower pressure end of the stability field of endmember deerite is thus located at an invariant point at 250±70°C and 10+-1.5 kbar. Deerite rich in the endmember can thus appear only in environments with geothermal gradients lower than 10°C/km and at pressures higher than about 10 kbar, which is in agreement with 4 out of 5 independent P-T estimates for known occurrences. The presence of such deerite places good constraints on minimum pressure and maximum temperature conditions. From log f _{O 2}-T diagrams constructed with the same data base at different pressures, it appears that endmember deerite is, at temperatures near those of its upper stability limit, stable only over a narrow range of oxygen fugacities within the magnetite field. With decreasing temperatures, deerite becomes stable towards slightly higher oxygen fugacities but reaches the hematite field only at temperatures more than 200°C lower than the upper stability limit. This practically precludes the coexistence deerite-hematite with near-endmember deerite in natural environments.     

The Pseudobrookite Group: Crystal Chemical Features of the Armalcolite Fe2+ Analogue

Doklady Earth Sciences - The crystal structure of a potentially new mineral, the Fe2+-dominant analogue of armalcolite with the idealized formula Fe2+Ti2O5 has been solved. The sample studied...     

钛掺杂磁铁矿吸附去除水中亚甲基蓝的研究

用一种新的合成方法在水相中合成了钛磁铁矿(Fe3-xTixO4),并用XRD和FTIR对已合成的Fe3-xTixO4进行了表征。结果表明:合成的Fe3-xTixO4为立方晶系尖晶石结构,样品中的钛离子都已经进入Fe3-xTixO4晶格中,且Fe3-xTixO4表面羟基量随着钛掺杂量的增加而增加。随后,以亚甲基蓝为模拟染料污染物,考察了Fe3-xTixO4的吸附性能。实验表明:钛掺杂能够显著促进Fe3-xTixO4对亚甲基蓝的吸附,吸附反应在0.5h内就能达到吸附平衡。     

Fe2+–Fe3+ ordered distribution in chromite spinels

Mossbauer measurements have been carried out on three natural chromite minerals from different locations in China over the temperature range 50 to 750 K. The experiments showed these samples to be magnesioferrochromites. The Mossbauer spectra measured could be decomposed into three doublets: two attributed to the tetrahedral T-site Fe²⁺ ions and the third to the octahedral M-site Fe³⁺ ions. Thus for the chromite spinels the results strongly supported the ordered distribution with Fe²⁺ in the T-site and Fe³⁺ in M-site.     

The crystal structure of sonoraite,Fe3+Te4+O3(OH)·H2O

Summary Sonoraite, FeTeO₃(OH)·H₂O, is monoclinic,P 2₁/c, witha=10.984(2),b=10.268(2),c=7.917(2) Å, =108.49(2)°. For 8 formula units per cell the calculated density is 4.179(2) g/cm³; the observed value is 3.95(1) g/cm³. The Supper-Pace automated diffractometer was used to collect 1884 independent reflections which were corrected for absorption. The structure was determined by an automated symbolic addition procedure. It was refined to a residualR of 6.2% using anisotropic temperature factors for the cations and isotropic temperature factors for the oxygen atoms. Chains of octahedra about Fe extend along [101]; edge-sharing pairs of these octahedra are joined by corner sharing. The Fe–Fe distances across the shared edges are 3.05 and 3.20 Å, short enough to suggest magnetic interactions. All but one H₂O are involved in the chains. The Te⁴⁺ ions have a pseudotetrahedral coordination, with three oxygen ions forming one face of the tetrahedron and the lone electron pair of Te occupying the fourth corner. The O–Te–O average bond angle is 95°. The Fe chains are tied together by Te–O bonds in all three dimensions.

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Die Kristallstruktur von Sonorait, Fe³⁺Te⁴⁺O₃(OH).H₂O

Zusammenfassung Sonorait, FeTeO₃(OH)·H₂O, ist monoklin, P 2₁/c, mit den folgenden Zelldimensionen:a=10,984(2),b=10,268(2),c=7,917(2) Å, =108,49(2)°. Mit 8 Formel-Einheiten errechnet man eine Dichte von 4,179(2) g/cm³; die gemessene Dichte beträgt 3,95(1) g/cm³. Das Supper-Pace automatische Diffraktometer wurde zur Sammlung von 1884 unabhängigen Reflexen benutzt, welche für Absorption korrigiert wurden. Die Struktur wurde mit Hilfe eines vollständig automatischen Programms für symbolische Addition bestimmt. Mit anisotropen Temperaturfaktoren für die Kationen und mit isotropen Temperaturfaktoren für die Sauerstoff-Atome wurde ein Residuum von 6,2% erreicht. Ketten von Eisen-Oktaedern erstrecken sich entlang [101]; Oktaeder-Paare mit gemeinsamen Kanten sind über Eckenverknüpfung verbunden. Die Fe–Fe-Abstände über die gemeinsamen Kanten betragen 3,05 und 3,20 Å, kurz genug, um zu magnetischer Wechselwirkung führen zu können. Nur ein H₂O-Molekül ist nicht Teil einer Kette. Die Te⁴⁺-Ionen befinden sich in pseudotetraedrischer Koordination; drei Sauerstoff-Ionen bilden eine Fläche des Tetraeders, die vierte Ecke wird durch das einsame Elektronenpaar von Te besetzt. Der Mittelwert des O–Te–O-Bindungswinkels beträgt 95° Die Fe-Ketten werden durch Te–O-Bindungen dreidimensional verbunden.

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With 3 Figures     

The Effects of Fe3? and Mn3? on Aluminum Silicate Phase Relations in North-Central New Mexico, U.S.A.

Aluminum silicate triple-point occurrences are common in metamorphicrocks of northern New Mexico. The three polymorphs show extensivesolid solution, with Fe and Mn substituting for Al. Mineraltextures, the spatial distribution of phases, and the systematicpartitioning of Fe and Mn indicate that the kyanite-andalusite-sillimaniteassemblages crystallized in equilibrium. The compositions ofminerals in the three-phase assemblage vary across the studyarea, recording regional variations in the pressures and temperaturesof metamorphism. The highest-pressure rocks, exposed at RioMora, contain kyanite at higher elevations and sillimanite atlower elevations. A sub-horizontal isograd separates the twominerals. Kyanite and sillimanite have nearly identical Fe contentwhich varies systematically with X_Fe2O3 in hematite or ilmenite.Andalusite occurs only along a single manganiferous layer, incrystals rich in MnAlSiO₅ and saturated in FeAlSiO₅. Triple-pointassemblages can be found wherever the folded manganiferous layercrosses the unfolded kyanite-sillimanite isograd. The TruchasRange, preserving slightly lower pressures of metamorphism,shows kyanite-andalusite-sillimanite in rocks with titaniferoushematite. Andalusite is enriched in Fe relative to kyanite andsillimanite, but no polymorphs contain Mn. Rocks with lowerX_Fe2O3 in hematite have kyanite and sillimanite without andalusite,whereas rocks with pure hematite contain only andalusite. Theshallowest erosional levels are preserved in the western PicurisRange where the three polymorphs occur as pure minerals in ilmenite-bearingrocks. Hematitic samples contain only andalusite which showsextensive solid solution of both Fe and Mn. The assemblage kyanite-andalusite-sillimanite is not invariant.Iron and manganese both add degrees of freedom. These transitionmetals have stabilized the three-phase assemblage, in apparentchemical equilibrium, across a P-T interval of 500-540 ?C, 3?8-4?6kb in rocks from New Mexico. The saturation level of FeAlSiO5in andalusite does not vary with Mn content but does vary withpressure and temperature. Calculations indicate that a 2-3 kbdecrease in pressure or a 25-50 ?C increase in temperature resultsin a 1 mole per cent increase in X_FeAlSiO5 in iron-saturatedandalusite.     

功能性Fe3O4磁纳米粒子的合成

本研究以PNIPAM(聚N-异丙基丙烯酰胺)为单体,先制备出来Fe3O4@SiO2纳米颗粒,再与DMP(十二烷基三硫代碳酸酯)链转移剂进行酯化反应,制备的产物作为新的链转移剂,在偶氮二异丁腈为引发剂的条件下,利用可逆加成-断裂链转移自由基聚合(RAFT)活性聚合法制备温度响应性磁纳米粒子。通过红外光谱法、核磁共振法对聚合物的结构进行表征,谱图表明成功地合成出所需的产物。通过扫描电镜对其进行分析,所得到的Fe3O4@SiO2-PNIPAM聚合物纳米颗粒分布比较均匀。