Kaolinite hydroxyls – a Raman microscopy study

Clay Minerals ◽  
1997 ◽  
Vol 32 (3) ◽  
pp. 471-484 ◽  
Author(s):  
R. L. Frost ◽  
S. J. van der Gaast

AbstractRaman microscopy of the kaolinite polymorphs was used to study single crystals and bundles of aligned crystals of kaolinite. The spectra of the hydroxyl stretching region were both sample and orientation dependent. Kaolinites can be classified into two groups according to the ratio of the intensities of the 3685 and 3695 cm−1 bands. No relationship was found between the d-spacing and the crystal domain size measurement from the 001 reflection and the Raman spectral intensities indicating the Raman spectra are independent of d-spacing and crystallinity. However, a relationship of the crystallinity in the a-b direction and intensities of the 3685 and 3695 cm−1 bands indicate that the relative position of one layer to the other determines the position of the inner surface hydroxyl groups and the hydrogen bonding with the oxygen of the opposite layer. A new hypothesis based on symmetric and non-symmetric hydrogen bonding of the inner surface hydroxyl groups is proposed to explain the two inner surface hydroxyl bands centred at 3685 and 3695 cm−1. The bands at 3670 and 3650 cm−1 are described in terms of the out-of-phase vibrations of the in-phase vibrations at 3695 and 3685 cm−1.

Clay Minerals ◽  
1997 ◽  
Vol 32 (4) ◽  
pp. 587-596 ◽  
Author(s):  
R. L. Frost ◽  
T. H. Tran ◽  
J. Kristof

AbstractChanges in the molecular structure of a highly ordered kaolinite, intercalated with urea and potassium acetate, have been studied using Raman microscopy. A new Raman band, attributed to the inner surface hydroxyl groups strongly hydrogen bound to the acetate, is observed at 3605 cm-1 for the potassium acetate intercalate with the consequential loss of intensity in the bands at 3652, 3670, 3684 and 3693 cm-1. Remarkable changes in intensity of the Raman spectral bands of the low-frequency region of the kaolinite occurred upon intercalation. In particular, the 144 and 935 cm-1 bands increased by an order of magnitude and were found to be polarized. These spectroscopic changes provide evidence for the inner surface hydroxyl group-acetate bond being at an angle approaching 90° to the 001 face. Decreases in intensity of the bands at 243, 271 and 336 cm-1 were observed. The urea intercalate shows additional Raman bands at 3387, 3408 and 3500 cm-1 which are attributed to N-H vibrations after formation of the urea-kaolinite complex. Changes in the spectra of the inserting molecules were also observed.


Clay Minerals ◽  
2000 ◽  
Vol 35 (2) ◽  
pp. 443-454 ◽  
Author(s):  
R. L. Frost ◽  
J. Kristof ◽  
E. Horvath ◽  
J. T. Kloprogge

AbstractKaolinite hydroxyls in dimethylsulphoxide-intercalated (DMSO-intercalated) kaolinites have been determined using Raman spectroscopy at 298 and 77 K. The inner surface hydroxyl frequencies at 3650, 3670, 3684 and 3693 cm-1 move to higher wavenumbers upon cooling to 77 K and are observed at 3659, 3676, 3692 and 3702 cm-1. The inner hydroxyl frequency is at 3620 cm-1 at 298 K and is at 3615 cm-1 at 77 K. Upon intercalation with DMSO, additional bands are found at 3660, 3536 and 3501 cm-1 for the low-defect kaolinite and at 3664, 3543 and 3509 cm-1 for the high-defect kaolinite at 298 K. The 3660 cm-1 band at 298 K is resolved into two bands at 3658 and 3663 cm-1 at 77 K for the low-defect kaolinite and these bands are assigned to the inner surface hydroxyl groups, hydrogen-bonded to the DMSO molecule. It is proposed that the DMSO molecule exists with two different orientations in the intercalate and these two molecular forms are differentiated by the OH-stretching bands of the inner surface hydroxyl groups. This band for the high-defect kaolinite is found at 3664 cm-1 at 298 K and resolves into two bands at 3664 and 3673 cm-1 at 77 K.


2017 ◽  
Vol 4 (12) ◽  
pp. 2388-2394 ◽  
Author(s):  
Chang Liu ◽  
Qingxin Ma ◽  
Hong He ◽  
Guangzhi He ◽  
Jinzhu Ma ◽  
...  

The structure and activity of surface hydroxyl groups determined the performance of TiO2 during NO2 reaction.


2021 ◽  
Author(s):  
◽  
Aaron Charles Small

<p>The development of novel hybrid materials of cellulose fibres and substrates with nanoparticles, conducting polymers and quantum dots, opens up novel application for new packaging materials and paper based products for the ‘smart packaging’ and ‘functional products’ areas that are emerging in the paper and packaging industries. Examples of these materials which have been developed here include cellulose fibres and substrates functionalised with magnetic nanoparticles, electrically conducting polypyrrole, and photoluminescent zinc sulfide quantum dots.  Such materials were synthesised and then characterised using Alternating Gradient Magnetometry (AGM), Atomic Absorption Spectroscopy (AA), Cotec Profilometer Measurements, DC Conductivity Measurements, Photoluminescence Spectroscopy (PL), Scanning Electron Microscopy (SEM), SQUID Magnetometry, Transmission Electron Microscopy (TEM), Vibrational Sample Magnetometry (VSM), X-ray Diffraction (XRD), X-ray Fluorescence (XRF) and X-ray Photoelectron Spectroscopy (XPS).  Ferrimagnetic magnetite nanoparticles (particle size 12-26 nm) were synthesised by a simple aqueous precipitation method and had a magnetic saturation of approximately 60 emu g⁻¹, a coercive field of approximately 12-120 Oe, and a remnant magnetisation of approximately 11 emu g⁻¹.  Magnetite coated Kraft fibres (1.2 – 3.15 wt. % Fe) were synthesised by adding a colloidal suspension of magnetite nanoparticles to a suspension of Kraft fibres. The fibres retained their inherent properties, such as tensile strength and flexibility, but inherited the magnetic properties of the magnetic nanoparticles. The nanoparticles remained unchanged on bonding - presumably through hydrogen bonding between the surface hydroxyl groups of the cellulose and the oxygen present in the magnetite.  Newsprint, Kraft Board and Cotton fabric were coated with polypyrrole using a chemical polymerisation method. SEM shows a complete coating, whereby the fibres are completely encapsulated by the polymer, including individual fibrils. Again, bonding is facilitated through hydrogen bonding between the surface hydroxyl groups of the cellulose and the lone pairs of the nitrogen in the polypyrrole backbone. Samples were doped with p-toluenesulfonic acid to increase conductivity, of which up to 4 S cm⁻¹ was achieved.  The samples were coated with magnetite nanoparticles using a starch binder, and tested for their application in EMI shielding. A maximum shielding effectiveness of 43 % in the 1-18 GHz range and 47 % in the 16-40 GHz range was obtained using cotton fabrics coated with both polypyrrole and magnetite. A synergistic effect is observed on using a polypyrrole and magnetite coating.  Photoluminescent ZnS quantum dots, synthesised using an aqueous precipitation method, were doped with Mn²⁺ and Cu²⁺ to achieve emissions at approximately 600 nm (Mn²⁺) and 530 nm (Cu²⁺) on irradiation with UV light. The quantum dots had a particle size of approximately 2 nm, and were present in the zinc blende phase.  Doped ZnS-coated Kraft fibres (5 – 30 wt. % Zn) were synthesised by a number of methods, the most successful being the ‘in-situ’ method, in which a uniform and complete coating was afforded. The fibres retained their inherent properties, such as tensile strength and flexibility, but inherited the photoluminescent properties of the ZnS quantum dots. The quantum dots remained unchanged on bonding - presumably through hydrogen bonding between the surface hydroxyl groups of the cellulose and the sulfur present in the ZnS quantum dots.  ZnS quantum dots doped with Mn² and Cu²⁺ were successfully formulated for inkjet printing by capping with mercaptosuccinic acid. Upon irradiation with UV light, emissions at approximately 600 nm (Mn²⁺-doped) and 530 nm (Cu²⁺-doped) were observed. These were successfully inkjet printed in intricate patterns onto a number of substrates, including photographic quality inkjet paper, cotton, and wool.</p>


2021 ◽  
Author(s):  
◽  
Aaron Charles Small

<p>The development of novel hybrid materials of cellulose fibres and substrates with nanoparticles, conducting polymers and quantum dots, opens up novel application for new packaging materials and paper based products for the ‘smart packaging’ and ‘functional products’ areas that are emerging in the paper and packaging industries. Examples of these materials which have been developed here include cellulose fibres and substrates functionalised with magnetic nanoparticles, electrically conducting polypyrrole, and photoluminescent zinc sulfide quantum dots.  Such materials were synthesised and then characterised using Alternating Gradient Magnetometry (AGM), Atomic Absorption Spectroscopy (AA), Cotec Profilometer Measurements, DC Conductivity Measurements, Photoluminescence Spectroscopy (PL), Scanning Electron Microscopy (SEM), SQUID Magnetometry, Transmission Electron Microscopy (TEM), Vibrational Sample Magnetometry (VSM), X-ray Diffraction (XRD), X-ray Fluorescence (XRF) and X-ray Photoelectron Spectroscopy (XPS).  Ferrimagnetic magnetite nanoparticles (particle size 12-26 nm) were synthesised by a simple aqueous precipitation method and had a magnetic saturation of approximately 60 emu g⁻¹, a coercive field of approximately 12-120 Oe, and a remnant magnetisation of approximately 11 emu g⁻¹.  Magnetite coated Kraft fibres (1.2 – 3.15 wt. % Fe) were synthesised by adding a colloidal suspension of magnetite nanoparticles to a suspension of Kraft fibres. The fibres retained their inherent properties, such as tensile strength and flexibility, but inherited the magnetic properties of the magnetic nanoparticles. The nanoparticles remained unchanged on bonding - presumably through hydrogen bonding between the surface hydroxyl groups of the cellulose and the oxygen present in the magnetite.  Newsprint, Kraft Board and Cotton fabric were coated with polypyrrole using a chemical polymerisation method. SEM shows a complete coating, whereby the fibres are completely encapsulated by the polymer, including individual fibrils. Again, bonding is facilitated through hydrogen bonding between the surface hydroxyl groups of the cellulose and the lone pairs of the nitrogen in the polypyrrole backbone. Samples were doped with p-toluenesulfonic acid to increase conductivity, of which up to 4 S cm⁻¹ was achieved.  The samples were coated with magnetite nanoparticles using a starch binder, and tested for their application in EMI shielding. A maximum shielding effectiveness of 43 % in the 1-18 GHz range and 47 % in the 16-40 GHz range was obtained using cotton fabrics coated with both polypyrrole and magnetite. A synergistic effect is observed on using a polypyrrole and magnetite coating.  Photoluminescent ZnS quantum dots, synthesised using an aqueous precipitation method, were doped with Mn²⁺ and Cu²⁺ to achieve emissions at approximately 600 nm (Mn²⁺) and 530 nm (Cu²⁺) on irradiation with UV light. The quantum dots had a particle size of approximately 2 nm, and were present in the zinc blende phase.  Doped ZnS-coated Kraft fibres (5 – 30 wt. % Zn) were synthesised by a number of methods, the most successful being the ‘in-situ’ method, in which a uniform and complete coating was afforded. The fibres retained their inherent properties, such as tensile strength and flexibility, but inherited the photoluminescent properties of the ZnS quantum dots. The quantum dots remained unchanged on bonding - presumably through hydrogen bonding between the surface hydroxyl groups of the cellulose and the sulfur present in the ZnS quantum dots.  ZnS quantum dots doped with Mn² and Cu²⁺ were successfully formulated for inkjet printing by capping with mercaptosuccinic acid. Upon irradiation with UV light, emissions at approximately 600 nm (Mn²⁺-doped) and 530 nm (Cu²⁺-doped) were observed. These were successfully inkjet printed in intricate patterns onto a number of substrates, including photographic quality inkjet paper, cotton, and wool.</p>


1998 ◽  
Vol 52 (10) ◽  
pp. 1277-1282 ◽  
Author(s):  
Ursula Johansson ◽  
Ray L. Frost ◽  
Willis Forsling ◽  
J. Theo Kloprogge

Raman spectroscopy of two types of kaolinites has been obtained at liquid nitrogen temperature (77 K) with the use of a Raman microprobe and a thermal stage. The Raman spectrum is characterized by the combination of the frequencies of the inner hydroxyl and the inner surface hydroxyl groups. The inner hydroxyl frequency is reduced, and the outer hydroxyl frequencies move to higher frequencies upon cooling to 77 K. The inner hydroxyl frequency shifts from 3620 cm−1 at 298 K to 3615 cm−1 at 77 K. The two in-phase inner surface hydroxyl frequencies move from 3684 and 3689 cm−1 at 298 K to 3690 and 3699 cm−1 at 77 K. The two out-of-phase vibrations shift from 3650 and 3668 cm−1 to 3656 and 3675 cm−1. The bandwidth of the inner hydroxyl frequency decreases from 3.7 to 2.1 cm−1 at 77 K. The bandwidth of the inner surface hydroxyl frequency ( v1) increases upon cooling from 17.4 to 19.2 cm−1. It is proposed that the increased resolution at low temperature enabled an additional inner surface hydroxyl frequency to be observed.


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