Department of Mineralogy, Petrography and Geochemistry

Department of Mineralogy, Petrography and Geochemistr

Na-montmorillonite modified with ammonium salts and azobenzene as a photoactive nanomaterial

Modification of inorganic solid structures (e.g. minerals) with organic molecules is a constantly developed topic in material sciences. The organic functionalization leads to the production of new materials with integrated properties of both the organic and inorganic component. In the presented study we have modified a Na-montmorillonite with alkylammonium surfactants and subsequently azobenzene, in order to obtain a nanomaterial that shows response to UV radiation. Azobenzene is a photoswitchable organic molecule capable to change its conformation upon UV radiation from the trans- to cis-azobenzene isomer. This reaction is coupled with a change of the molecules shape and dimensions (Klajn 2010). The montmorillonite is a layered aluminosilicate that serves as an excellent host structure for organic guest species. Due to the net negative layer charge it shows the ability to swell and to exchange the originally present interlayer cations. These properties allow the intercalation of bulk organic molecules and to control their arrangement. Much attention has been paid to the possibility of transferring the photoswitching ability of organic molecule into the motion of the whole organo-mineral structure (Heinz et al. 2008). Such nanoswitch is particularly appealing as it is controlled with radiation – remotely and at a precise location. The efficiency of a synthesized nanoswitch depends on an accurate selection of the host and guest component. The target of this study to test a series of organic surfactants and to establish a modification pathway that leads to obtaining a material most promising in the view of its photoresponsive behavior. The montmorillonite modification was performed in a two-step procedure, as the direct intercalation of a nonionic azobenzene is not possible. First, the Na-montmorillonite (denoted SWy) was ion-exchanged with trimethylalkylammonium cations abbreviated C n and benzyldimethylalkylammonium cations – BC n , where n refers to the number of carbon atoms in the alkyl chain and is equal to 12, 14 or 16. In the second step the organo-montmorillonites were reacted with azobenzene (AzBz) for 24 h at 120°C in a hermetically closed teflon vessel. The yellowish products were characterized with the X-Ray diffraction (XRD), the infrared spectroscopy (FTIR) and CHN elemental analysis. In all cases the intercalation of the ammonium cation caused an increase of the montmorillonites basal spacing ( d 001 ). The d 001 values were equal to 16.4 Å, 18.2 Å and 20.5 Å for SWy-C 12 , SWy-C 14 and SWy-C 16 , respectively. The samples modified with the BC n cations showed ~1.5 Å larger basal spacing, due to the presence of the benzyl group in the intercalated molecule. A linear relationship was observed between the d 001 value and the alkyl chain length of the introduced salts. This suggests that the organic cations formed paraffin-type aggregates in the interlayer (Ogawa et al. 1999) where the molecules are inclined to the layer surface. The FTIR spectra of modified SWy sample showed intense bands corresponding to CH 2 vibration modes. Along with the increasing alkyl chain length the CH 2 stretching bands shifted towards lower energies. This is an effect of growing packing density of alkylammonium molecules in the interlayer (He et al. 2004) and it is coupled with straightening of the alkyl chains due to transformation of disordered gauche conformer to the ordered all-trans conformer (Vaia et al. 1994). It can be concluded that the longer alkyl chains (C 16 and BC 16 ) form more ordered, solid-like aggregates in the interlayer space. The molar content of organic molecules was calculated basing on the CHN elemental analysis. The amount of intercalated alkylammonium cations was nearly equal to the cation exchange capacity (CEC) of montmorillonite – 88.9 meq/100 g. The reaction with azobenzene was most effective for montmorillonite modified with the alkylammonium cations having the longest chains as confirmed by the XRD patterns. The d 001 values of SWy-C 16 and SWy-BC 16 samples after reaction with AzBz increased to 36.9 Å and 35.9 Å, respecively. Well resolved and intense (001) peaks as well as the presence of the 2 nd and 3 rd order reflections indicated a highly ordered structure of these intercalates. On the contrary, diffraction peaks were less resolved and broadened for samples prepared with the shorter C 12 , C 14 , BC 12 and BC 14 molecules after reaction with AzBz. Based on these results, it is assumed that the long chain alkylammonium ions are more effective surfactants for the further intercalation of azobenzene into the montmorillonites interlayer space. The obtained highly ordered structures are promising materials for application as photo-actuated nanoswitches

Preparation and characterization of azobenzene-smectite photoactive mineral nanomaterials

Smectites are 2:1 layered minerals built of one octahedral sheet located between two tetrahedral sheets. The layer charge, derived from the isomorphic substitutions in the mineral structure, is compensated by the interlayer cations. The capability to exchange the interlayer cations is an important property of smectites as it enables to design and produce new nanomaterials based on natural minerals through their organic modification. Such hybrid materials are highly desirable in industry and environmental protection due to their specific properties that may be controlled in nanoscale. Preparation of photoactive materials through intercalation of layered minerals, including mainly synthetic micas, with azobenzene and other azo-compounds was proposed previously (Fujita et al., 2003; Ogawa et al., 2003; Heinz et al., 2008). Azobenzene molecules show a change in their shape and dimensions upon the UV irradiation, which may affect the structure of host mineral. The photoactivate materials may find application in nanotechnology as molecular nanoswitches and nanosensors controlled by UV radiation. The objective of the study was to prepare azobenzene-smectite intercalation compounds. The obtained materials were subjected to structural and chemical characterization, which is crucial for further advancement of their photoresponsive properties. Na-montmorillonite (SWy), Ca-montmorillonite (STx), beidellite (BId) and synthetic laponite (SynL) were used for the experiments. The modification procedure involved at first the intercalation of smectites with hexadecyltrimethylammonium bromide (abbreviated C16) and after that the insertion of azobenzene into the interlayer space. The reaction with C16, in amount equal to 1.0 CEC of the smectite, was performed in an aqueous suspension (20g/L) for 2 h in 60°C. The obtained organo-smectites were prepared as thin films on glass plates and reacted with azobenzene in a teflon vessel at ~100°C for 24 h.In such conditions the azobenzene vaporizes and penetrates the interlayer space of the organo-mineral. The azobenzene/smectite weight ratio was equal to 0.2. The chemical and structural analysis of all obtained samples was carried out with use of X-ray diffraction  (XRD), infrared spectroscopy (FTIR) and CHN elemental analysis. The increased amount of nitrogen and carbon in modified samples confirmed the occurrence of intercalation process of both the ammonium salt and the azobenzene. Moreover, new bands appeared in the infrared spectra of the C16-smectites at ~2924 cm-1 and ~2851 cm-1 due to the C-H stretching vibrations in the C16 molecules. The spectra of azobenzene intercalation compounds showed additionally a series of bands corresponding to the vibrations characteristic for the azobenzene molecule at: ~3061 cm-1, ~1581 cm-1, ~1455 cm-1, and ~1302 cm-1. . The basal spacing of tested minerals increased after the C16 intercalation, as confirmed by the XRD analysis. The increase was equal to 6.1 Å, 3.3 Å, 4.1 Å and 3.5 Å for SWy, STx, BId and SynL samples, respectively. This suggests a nearly horizontal arrangement of C16 molecules and formation of a monolayer in the interlayer space of smectite. Introduction of azobenzene lead to a further increase of d001 value. The increase is visibly different for all the samples and is equal to 7.0 Å, 15.0 Å, 21.7 Å and 23.5 Å for SWy, STx, BId and SynL samples, respectively. The arrangement of organic molecules in the interlayer space is influenced by a number of factors including: the type of the mineral, the layer charge and its location in the layer, or the amount and arrangement of the cationic surfactant. A correlation between the azobenzene location in the interlayer space and the photoresponse behavior of tested materials will be the subject of further studies

A comparative study on the removal of Pb(II), Zn(II), Cd(II) and As(V) by natural, acid activated and calcined halloysite

Trace elements like lead, zinc, cadmium and arsenic are among the most hazardous for the environment. They tend to accumulate in living organisms and exhibit carcinogenic or toxic properties. With the intensive development of the global industry these elements spread and infiltrate into soil and water, what results in contamination. Clay minerals play an important role in the environment as natural adsorbents. This is due to their ability of attracting ions from water solutions. The contaminants are accumulated by the structure of clay minerals, which leads to their immobilization. Halloysite is a clay mineral, belonging to the kaolin group minerals. Its structure is composed of stacked 1:1 layers built from octahedral (alumina) and tetrahedral (silica) sheets, linked through hydrogen bonds. Due to the fact that Poland has several kaolin deposits it is important to undertake research concerning possibility of using them as a natural scavenger of pollutants (Matusik & Bajda 2013, Matusik & Wścisło 2014). Thus, the purpose of the research was to investigate the sorption affinity of natural, acid activated and calcined halloysite toward Pb(II), Zn(II), Cd(II) and As(V). In the study three mineral samples were chosen: natural halloysite – H, acid activated halloysite – HA and calcined halloysite – HC. The H sample used in the study came from Polish deposit located in Dunino near Legnica which is owned and exploited by the Intermark company. The last two samples are produced by Intermark on an industrial scale, by modifying H sample. The materials were characterized using XRD and FTIR methods. Additionally the cation exchange capacity (CEC) and specific surface area (SBET) were measured. The CEC of tested materials were measured by adsorption of methylene blue. The SBET was determined on the basis of the low temperature nitrogen adsorption isotherm measured at -196°C and calculated in accordance with the Brunauer-Emmet-Teller (BET) methodology. The materials sorption affinity towards Pb(II), Zn(II), Cd(II) and As(V) was investigated. Experiments were carried out at pH 5. After mixing 50 mg of each material with 2.5 ml of appropriate solution (20 g/L - solid/solution ratio), sample portions were shaken for 24 h at room temperature to reach equilibrium. The concentration of metals – Pb(II), Cd(II) and Zn(II) in supernatant solutions was determined using AAS method while the As(V) was measured using colorymetric molybdenum blue method. The XRD pattern of the H sample showed a basal peak at 7.20 Å, which is attributed to dehydrated halloysite-7(Å). There were no significant changes in the XRD pattern of HC sample, which indicated that there were no serious changes in the clay structure due to calcined. In contrast, the XRD pattern of HA sample showed a decrease in intensity of ~7.20 Å peak of halloysite and the appearance of new peak at 7.63 Å was observed. Also, there were changes in the 19-25°2θ region, what is an effect of structural disorder caused by sulfuric acid treatment. It is worth notifying that the FTIR spectra of H and HC samples did not differ significantly. In turn, the bands changes for the HA are noticeable, which is in accordance with XRD results. After acid treatment the bands shape and intensity in 1300-1000 cm-1 region has changed indicating structural disorder of tethraedral sheet. The spectra revealed that the octahedral sheet and OH hydroxyls were not significantly altered. The HA sample exhibited the largest SBET (171.6 m2/g) while the SBET for the H sample was the lowest (49.5 m2/g). The calcination led to slight increase of SBET value to 52.1 m2/g in comparison to the H sample. The CEC results showed that differences between H (8.79 meq/100 g) and HC (8.19 meq/100 g) samples are insignificant, moreover the CEC of H sample is slightly higher. Such decrease can be explained by the loss of some the cation exchange sites, induced by heat treatment (Ho & Handy 1964). The enhancement in CEC was observed for the HA sample (10.69 meq/100 g). Sorption mechanism for raw halloysite can take place via ion-exchange and surface complexation through silanol Si-OH and aluminol Al-OH groups. The Pb(II) ions are more likely to hydrolyze and create PbOH+ forms, which may link to deprotonated groups. This process is called surface complexation. Heavy metals such as Zn(II) and Cd(II) tend to adsorb through ion-exchange. The adsorption behavior of tested heavy metals onto tested materials differs. The sorption capacity for H sample was found to follow the sequence As(V)>Pb(II)>Cd(II)>Zn(II). In the case of cations, this behavior reflects the cations hydrolysis constants, which are equal to 7.71, 8.96, and 10.08 respectively. The sorption capacity for H sample reached 168.4 mmol As/kg, 37.2 mmol Pb/kg, 3.7 mmol Cd/kg and 1.9 mmol Zn/kg. The sorption onto HC sample was found to be the following: Pb(II)≈Zn(II)>Cd(II)>As(V). Comparing sorption results for HC to the results for H sample, the increase of sorption for all tested heavy metals was observed. The sorption of cations reached an equilibrium equal to: 219 mmol Pb/kg, 212 mmol Zn/kg and 134.4 mmol Cd/kg. The sorption of As(V) decreased slightly in comparison to H sample. The acid activation resulted in an increase of active sites capable for Pb(II) adsorption and a decrease of active sites responsible for As(V) adsorption. Sorption equilibrium reached 235 mmol Pb/kg and 66 mmol As/kg. The results obtained for Zn(II) and Cd(II) indicated that sorption was not observed which may be due to lack of ion-exchange sites. The explanation of this behavior requires further studies. It is was worth to underline the highest sorption capacity of H sample towards As(V) which is most likely due to surface complexation. The results indicated that depending on the type of pollutants an appropriate type of halloysite-based sorbent needs to be chosen.   This project was supported by the Polish National Science Centre under research project awarded by decision No. DEC-2011/01/D/ST10/06814.Trace elements like lead, zinc, cadmium and arsenic are among the most hazardous for the environment. They tend to accumulate in living organisms and exhibit carcinogenic or toxic properties. With the intensive development of the global industry these elements spread and infiltrate into soil and water, what results in contamination. Clay minerals play an important role in the environment as natural adsorbents. This is due to their ability of attracting ions from water solutions. The contaminants are accumulated by the structure of clay minerals, which leads to their immobilization. Halloysite is a clay mineral, belonging to the kaolin group minerals. Its structure is composed of stacked 1:1 layers built from octahedral (alumina) and tetrahedral (silica) sheets, linked through hydrogen bonds. Due to the fact that Poland has several kaolin deposits it is important to undertake research concerning possibility of using them as a natural scavenger of pollutants (Matusik & Bajda 2013, Matusik & Wścisło 2014). Thus, the purpose of the research was to investigate the sorption affinity of natural, acid activated and calcined halloysite toward Pb(II), Zn(II), Cd(II) and As(V). In the study three mineral samples were chosen: natural halloysite – H, acid activated halloysite – HA and calcined halloysite – HC. The H sample used in the study came from Polish deposit located in Dunino near Legnica which is owned and exploited by the Intermark company. The last two samples are produced by Intermark on an industrial scale, by modifying H sample. The materials were characterized using XRD and FTIR methods. Additionally the cation exchange capacity (CEC) and specific surface area (SBET) were measured. The CEC of tested materials were measured by adsorption of methylene blue. The SBET was determined on the basis of the low temperature nitrogen adsorption isotherm measured at -196°C and calculated in accordance with the Brunauer-Emmet-Teller (BET) methodology. The materials sorption affinity towards Pb(II), Zn(II), Cd(II) and As(V) was investigated. Experiments were carried out at pH 5. After mixing 50 mg of each material with 2.5 ml of appropriate solution (20 g/L - solid/solution ratio), sample portions were shaken for 24 h at room temperature to reach equilibrium. The concentration of metals – Pb(II), Cd(II) and Zn(II) in supernatant solutions was determined using AAS method while the As(V) was measured using colorymetric molybdenum blue method. The XRD pattern of the H sample showed a basal peak at 7.20 Å, which is attributed to dehydrated halloysite-7(Å). There were no significant changes in the XRD pattern of HC sample, which indicated that there were no serious changes in the clay structure due to calcined. In contrast, the XRD pattern of HA sample showed a decrease in intensity of ~7.20 Å peak of halloysite and the appearance of new peak at 7.63 Å was observed. Also, there were changes in the 19-25°2θ region, what is an effect of structural disorder caused by sulfuric acid treatment. It is worth notifying that the FTIR spectra of H and HC samples did not differ significantly. In turn, the bands changes for the HA are noticeable, which is in accordance with XRD results. After acid treatment the bands shape and intensity in 1300-1000 cm-1 region has changed indicating structural disorder of tethraedral sheet. The spectra revealed that the octahedral sheet and OH hydroxyls were not significantly altered. The HA sample exhibited the largest SBET (171.6 m2/g) while the SBET for the H sample was the lowest (49.5 m2/g). The calcination led to slight increase of SBET value to 52.1 m2/g in comparison to the H sample. The CEC results showed that differences between H (8.79 meq/100 g) and HC (8.19 meq/100 g) samples are insignificant, moreover the CEC of H sample is slightly higher. Such decrease can be explained by the loss of some the cation exchange sites, induced by heat treatment (Ho & Handy 1964). The enhancement in CEC was observed for the HA sample (10.69 meq/100 g). Sorption mechanism for raw halloysite can take place via ion-exchange and surface complexation through silanol Si-OH and aluminol Al-OH groups. The Pb(II) ions are more likely to hydrolyze and create PbOH+ forms, which may link to deprotonated groups. This process is called surface complexation. Heavy metals such as Zn(II) and Cd(II) tend to adsorb through ion-exchange. The adsorption behavior of tested heavy metals onto tested materials differs. The sorption capacity for H sample was found to follow the sequence As(V)>Pb(II)>Cd(II)>Zn(II). In the case of cations, this behavior reflects the cations hydrolysis constants, which are equal to 7.71, 8.96, and 10.08 respectively. The sorption capacity for H sample reached 168.4 mmol As/kg, 37.2 mmol Pb/kg, 3.7 mmol Cd/kg and 1.9 mmol Zn/kg. The sorption onto HC sample was found to be the following: Pb(II)≈Zn(II)>Cd(II)>As(V). Comparing sorption results for HC to the results for H sample, the increase of sorption for all tested heavy metals was observed. The sorption of cations reached an equilibrium equal to: 219 mmol Pb/kg, 212 mmol Zn/kg and 134.4 mmol Cd/kg. The sorption of As(V) decreased slightly in comparison to H sample. The acid activation resulted in an increase of active sites capable for Pb(II) adsorption and a decrease of active sites responsible for As(V) adsorption. Sorption equilibrium reached 235 mmol Pb/kg and 66 mmol As/kg. The results obtained for Zn(II) and Cd(II) indicated that sorption was not observed which may be due to lack of ion-exchange sites. The explanation of this behavior requires further studies. It is was worth to underline the highest sorption capacity of H sample towards As(V) which is most likely due to surface complexation. The results indicated that depending on the type of pollutants an appropriate type of halloysite-based sorbent needs to be chosen. This project was supported by the Polish National Science Centre under research project awarded by decision No. DEC-2011/01/D/ST10/06814

Removal of selected anions by raw halloysite and smectite clay

The structure of clay minerals is made up from tetrahedral and octahedral sheets, which can be stacked in different ways, forming 1:1, 2:1 and 2:1:1 layers. Halloysite, which belongs to the kaolin group, is composed of 1:1 layers while smectite group minerals exhibit 2:1 dioctahedral layered structure. The most important feature of these minerals is the presence of numerous active centers on their surface and/or in the interlayer space, which allows them to attract and exchange ions from aqueous solutions. These makes them perfect candidates which could be used for the purification of wastewaters from harmful ions (Bhattacharyya & Gupta 2008; Lee & Tiwari 2012). The aim of this work was to examine the sorption capacity of natural halloysite and smectite clay towards P(V), As(V) and Cr(VI). Two samples used in the research came from Polish deposits. Natural halloysite (H) was obtained from Dunino deposit, while smectite clay (SC) was obtained from Bełchatów Lignine Mine where it forms an overburden cover. For the both raw samples the XRD patterns and FTIR spectra were collected. The sorption of P(V), As(V) and Cr(VI) was conducted as a function of anions concentration in the range from 0.05 to 50 mmol/L for initial pH 5 in a single-element system. The suspension of H or SC and an adequate solution (solid/solution ratio: 20 g/L) was shaken for 24 h at 25°C. Afterwards the anions concentration in the supernatant solution was measured using colorimetric methods. The P(V) and As(V) concentration was determined with molybdenum blue method, while Cr(VI) concentration was measured with diphenylcarbazide method. The XRD pattern of the H sample showed a basal peak at 7.20 Å, which confirms the presence of dehydrated halloysite-(7 Å). In turn, the SC exhibited a peak centered at ~12.5 Å with an asymmetric profile starting from ~15.0 Å. Such reflection suggests the presence of smectite which has both Na+ and Ca2+ cations in its interlayer space. The peaks at 4.26 Å and 3.34 Å are associated with quartz. The IR spectra of the H showed bands characteristic for kaolin group minerals related to the OH-stretching region (3700-3620 cm-1), vibrations of water molecules (~1630 cm-1) and bands assigned to stretching and bending vibrations of aluminosilicate framework (1200-400 cm-1). The IR spectrum of SC shows bands characteristic for smectite minerals i.e. 3623 cm-1 band attributed to OH hydroxyl located inside the 2:1 layer and a broad band centered at ~3400 cm-1 due to interlayer water surrounding cations. Also the structural vibrations of the 2:1 layer may be observed in the 1200-400 cm-1 region. The results of the experiment indicated that the sorption capacity of the H sample and the SC sample were relatively high. The amount of removed P(V) was the highest for both materials, where the sorption was respectively equal to: 201 and 256 mmol/kg. The sorption capacity of As(V) for the H was equal to 168 mmol/kg, while it was significantly lower on the SC (96 mmol/kg). In the case of H the Cr(VI) sorption reached only 36 mmol/kg and for the SC it was equal to 104 mmol/kg. In most cases the sorption isotherms were fitted to the Freundlich model. The only exception was for P(V) sorption on the H sample, which was better described by Langmuir model. The specific surface areas (SBET) of the studied materials do not differ significantly: SC = 69.10 m2/g and H = 49.52 m2/g. The sorption centers that may attract anions in both, H and SC samples, were limited, because isomorphic substitutions in tetrahedral and/or octahedral sheets generate positively charged sites, which attract cations. It is believed that the mechanism responsible for the adsorption of anions on both materials is mainly surface complexation, which occurs at the crystals edges (Bradl 2004). The sorption capacity of the H and the SC was significantly lower than that reported for hydrotalcite-based anion-exchange materials (HTLc). For comparison, the sorption capacity towards P(V), As(V) and Cr(VI) on uncalcined HTLc was as follows: 498 mmol/kg (Kuzawa et al. 2006), 596 mmol/kg (Wu et al. 2013) and 314 mmol/kg (Alvarez-Ayuso & Nugteren 2005). Nevertheless, the examined mineral samples might be useful as sorbents for industrial wastewater treatment involving the removal of P(V) and As(V)

Clinical classification of rare cardiac arrhythmogenic and conduction disorders, and rare arrhythmias

Rare cardiovascular diseases and disorders (RCDDs) constitute an important clinical problem, and their proper classification is crucial for expanding knowledge in the field of RCDDs. The aim of this paper is to provide an updated classification of rare arrhythmogenic and conduction disorders, and rare arrhythmias (RACDRAs). We performed a search for RACDRAs using the Orphanet inventory of rare diseases, which includes diseases with a prevalence of no more than 5 per 10 000 in the general population. We supplemented this with a search of PubMed and Scopus databases according to a wider definition proposed by the European Parliament and the Council of the European Union. RACDRAs are categorized into 2 groups, primary electrical disorders of the heart and arrhythmias in specific clinical settings. The first group is further divided into subgroups of major clinical presentation: disorders predisposing to supraventricular tachyarrhythmias, ventricular tachyarrhythmias, bradyarrhythmias, and others. The second group includes iatrogenic arrhythmias or heart rhythm disturbances related to medical treatment, arrhythmias associated with metabolic disorders, and others. We provide a classification of RACDRAs and supplement them with respective RCDDs codes. The clinical classification of RACDRAs may form a basis to facilitate research and progress in clinical practice, both in diagnostic and therapeutic approaches

Special Issue: Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites

LDHs are a class of two-dimensional layered anionic structures with unique properties [...

Delaminacja i transformacja morfologii minerałów z grupy kaolinitu

Tyt. z nagłówka.Bibliogr. s. 2-3.Dostępny również na CD.SŁOWA KLUCZOWE: minerały, delaminacja, morfologia. KEYWORDS: minerals, morphology, delamination

Minerały z grupy kaolinitu jako prekursory nanorurek mineralnych rozprawa doktorska /

Tyt. z ekranu tytułowego.Praca doktorska. Akademia Górniczo-Hutnicza im. Stanisława Staszica (Kraków), 2010.Zawiera bibliogr.Dostępna także w wersji drukowanej.Tryb dostępu: Internet.Właściwości minerałów kaolinitowych, sposoby ich modyfikacji, charakterystyka minerałów z grupy kaolinitu, skład chemiczny, struktura, morfologia, geneza, występowanie w Polsce, tradycyjne zastosowania minerałów z grupy kaolinitu, sposoby modyfikacji, reakcje zachodzące na powierzchni, adsorpcja, grafting, reakcje zachodzące w przestrzeni międzypakietowej, interkalacja, nanokompozyty minerał-polimer, aktywacja kwasowa, termiczna, reakcje prowadzące do delaminacji, transformacji morfologii, odczynniki chemiczne, sprzęt laboratoryjny, sposób otrzymywania nanorurek mineralnych, synteza kompleksów minerałów z sulfotlenkiem dimetylu, K-DS, K-DS2, interlaminarny grafting minerałów przy użyciu 1,3-butanodiolu, metanolu, K-B, K-M, interkalacja minerałów przy użyciu heksyloaminy, oktadecyloaminy, K-HX, K-BHX, K-MHX, K-MOD, deinterkalacja minerałów interkalowanych aminami, K-T, K-HT, K-MOT, sposób otrzymywania nanokompozytów polimer-kaolinit, metody analityczne, dyfraktometria rentgenowska, XRD, spektroskopia absorpcyjna w podczerwieni, FTIR, metody termiczne, DTA, DSC, TG, mikroskopia elektronowa, SEM, TEM, badania tekstury metodą adsorpcji, desorpcji azotu, analiza wielkości uziarnienia, mikroskopia sił atomowych, AFM, wyznaczanie parametrów mechanicznych nanokompozytów polimerowych, wyznaczanie kąta zwilżania nanokompozytów polimerowych, badanie chropowatości powierzchni nanokompozytów polimerowych, charakterystyka materiałów wyjściowych, strukturalna, uziarnienia, tekstury, eksperyment, otrzymywanie nanorurek mineralnych, synteza interkalatów minerałów z sulfotlenkiem dimetylu, K-DS, interlaminarny grafting interkalatów K-DS przy użyciu 1,3-butanodiolu, K-B, interkalacja kompleksów K-DS przy użyciu heksyloaminy, K-HX, interkalacja kompleksów K-B przy użyciu heksyloaminy, K-BHX, deinterkalacja pochodnych K-BHX, K-T, obserwacje morfologii produktów końcowych eksperymentu, otrzymywanie nanorurek mineralnych, synteza interkalatów minerałów z sulfotlenkiem dimetylu przy wykorzystaniu promieniowania mikrofalowego, K-DS2, interlaminarny grafting interkalatów K-DS2 przy użyciu metanolu, K-M, interkalacja kompleksów K-M przy użyciu heksyloaminy, K-MHX, interkalacja pochodnych K-MHX przy użyciu oktadecyloaminy, K-MOD, deinterkalacja pochodnych K-MHX, K-MOD, K-HT, K-MOT, obserwacje morfologii produktów końcowych eksperymentu, delaminacja, zmiany strukturalne minerałów z grupy kaolinitu, charakterystyka teksturalna otrzymanych materiałów mineralnych, pochodne kaolinitu Maria III, <2 μm, MT, MHT, MMOT, <40 μm, M40T, M40HT, M40MOT, Jaroszów, <2 μm, JT, JHT, JMOT, haloizytu Dunino, <2 μm, HT, HHT, HMOT, nanokompozyty polimer-kaolinit, właściwości mechaniczne, powierzchniowe, charakterystyka strukturaln