Abstract: The present disclosure relates to a provide a method of synthesis of coated textiles from natural rubber with lignin and molybdenum disulfide for biomedical and protective applications and a composition thereof. The present invention discloses fabrication of biocompatible NR latex with Molybdenum disulfide (MoS2) nanosheets and lignin resulting in a coated textiles which is hydrophilic, antimicrobial, wound healing, acid resistance, UV blocking, flame retardant, and self-cleaning fabrics via a simple dipping method. The prepared coated textile samples find numerous applications in various biomedical purposes and can also be used as a protecting material. Figure 1
Description:FIELD OF THE INVENTION
The present invention relates to a method of synthesis of coated textile. More particularly, the present invention relates to a method of synthesis of coated textiles from natural rubber latex (NRL) with lignin and molybdenum disulfide (MoS2) for biomedical and protective applications and a composition thereof.
BACKGROUND OF THE INVENTION
The textile industry assumes an imminent role in the development of a country by contributing significantly to industrial output, export earnings, and generation of employment opportunities. The textile industry produces various products via natural or synthetic processes. Medical textiles, a combination of medical sciences and textile sciences, represent one of the fast-growing divisions within the textile industry. These textiles find application in numerous medical contexts, including wound dressings, drug delivery, tissue engineering, implantable medical devices, smart textiles, chemical and biological protective clothing, and more. These materials in medical applications should exhibit durability, flexibility, mechanical strength, biocompatibility, and non-toxic, antibacterial, and non-allergic properties. Medical textiles should exhibit resistance to microorganisms, acids, and alkalis. Medical textiles are classified into four categories: implantable, non-implantable, extracorporeal devices, and hygiene and healthcare materials.
Deposition of polymer or nanoparticle containing polymer dispersion on one or two sides of the fabric not only forms a coating over the yarns but also fills the gap between the yarns.
Polymer coating on textile materials improves their overall performance, conserving their visual appearance and increasing their lifetime, thus protecting materials for the
fabrics.
Polyurethane, Polyvinyl chloride, Polyacrylate, Polyvinyl acetate, polyvinyl alcohol (PVA), epoxy, rubber, etc., are some of the most common polymers used for textile coating.
Polymer coatings can provide various functional properties, and the final coated textiles will be flame retardant, antimicrobial, thermally stable, breathable, waterproof, lightproof and durable. Polymer-coated textiles have many applications like medical, protective materials, agriculture, aerospace, geotextiles, transportation, sports, packaging, etc.
Molybdenum disulfide is an inorganic compound containing molybdenum and sulfur coming under the transition metal dichalcogenides family. It is used as an alternative to graphite due to its structural and electronic similarity. Two planes of sulfur atoms and one plane of molybdenum atoms are stacked one above another using robust covalent interactions, and the layers are interconnected by weak van der Waals interactions. MoS2 can be synthesized with various morphologies like nanosheets, flower-like particles, quantum dots, nanotubes etc. MoS2 nanomaterials play a major role in catalysis, sensors, biomedical applications, environmental applications, energy storage, optoelectronics etc.
MoS2 is a widely used material for various biomedical applications like drug delivery, photothermal therapy, tissue engineering, bioimaging, biosensing, etc. In addition, MoS2 can act as an antibacterial and reinforcing agent for various polymer matrices. Bulk MoS2 can be converted into nanosheets by overcoming the van der Waals interactions existing among the layers.
Lignin is an important complex, organic, and oxygen-containing biopolymer found in wood, which gives structural support and protects the plant from microorganisms.
Comprising three complex polymers, lignin stands as the second most prevalent material, following cellulose. It is a biodegradable, antimicrobial, non-toxic, biocompatible, UV absorbing material. Moreover, lignin is an excellent reinforcing agent for numerous polymers.
Lignin is a waste product in the paper industry because it is removed from the pulp during paper production. Thus, effective isolation and further use of lignin can reduce waste during paper production. The scientific community has been focusing more on converting macro lignin into nano form to expand its applications in more areas.
Lignin can be converted into nano lignin by solvent exchange, homogenization, sonication, etc., and the formed nano lignin can be used as reinforcing filler in many polymers.
As mentioned earlier, rubber can be used as a textile coating material. Among various rubber matrices, natural rubber latex is the more appropriate polymer for textiles because of its availability, easy processing, eco-friendliness, biocompatibility, etc.
NRL is a colloidal dispersion of rubber particles in water extracted from the Hevea brasiliensis or rubber tree through tapping. In addition to rubber hydrocarbons, NRL contains 4-5% of nonrubber components such as proteins, lipids, fatty acids, etc. Das et al. demonstrated the fabrication of a blend of PVA, NRL, and starch-coated cotton fabrics with breathability, waterproofness, and mechanical properties.
There are a number of patents and non-patents literature discussing the said domain of the sciences. One such non-patent literature is Habeeba et al. which discloses immobilized chitosan on cotton material using NRL. The prepared chitosan containing NRL -coated cotton fabrics was hydrophilic and showed antibacterial action. In another study, modified chitosan stabilized silver nanoparticles incorporated NRL coated on cotton fabrics, enhancing the cotton's mechanical, antibacterial properties, and hydrophobicity.
Sodium lignosulfonate (SLS) enhanced the interface bonding between the NRL and wool. After the SLS treatment, water diffusion properties were reduced, and mechanical properties were found to increase.
NRL-containing nanofiller coated fabrics are not disclosed in the prior art. not much developed. To our knowledge, no works have been reported on MoS2 and lignin-containing NRL-coated fabrics. Most of the existing state of art disclose NR nanocomposites which are designed to use in mechanical property related applications and biomedical applications of NR nanocomposites are also less reported.
To overcome the drawbacks associated with the existing state of art, the present invention discloses the synthesis and composition of NRL-containing nanofiller coated fabrics which are hydrophilic, antibacterial, self-cleaning, wound healing, UV-blocking latex-coated textiles containing lignin and MoS2 through a simple and green method.
OBJECT OF THE INVENTION:
One of the main objects of the invention is to provide a method of synthesis of coated textile.
Yet another object of the present invention is to provide a method of synthesis of coated textiles from natural rubber latex with lignin and molybdenum disulfide for biomedical and protective applications.
Yet another object of the present invention is to provide a method which is scalable, cost effective and rapid for preparing coated textiles.
Yet another object of the present invention is to provide NRL-containing nanofiller coated fabrics which are hydrophilic, antibacterial, self-cleaning, wound healing, UV-blocking.
Yet another object of the present invention is to provide a green method of synthesis of coated textiles from natural rubber with lignin and molybdenum disulfide for biomedical and protective applications
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a method of synthesis of coated textile. The present invention relates to a method of synthesis of coated textiles from natural rubber latex with lignin and molybdenum disulfide for biomedical and protective applications and a composition thereof.
The present invention provides a method of synthesis of coated textile by insertion of various nanofillers into Natural Rubber Latex (NRL) which improves and introduces new properties to final natural rubber nanocomposites. NRL containing nanofiller dispersion is found to be an efficient coating material for textile materials. Multifunctional textile material can be fabricated by coating with a hybrid nanofiller system containing NRL dispersion; thereby, the utility of the final textile materials can have applications in many fields rather than one area. The present invention discloses fabrication of biocompatible NRL with Molybdenum disulfide (MoS2) nanosheets and lignin resulting in a coated textiles which is hydrophilic, antimicrobial, wound healing, acid resistance, UV blocking, flame retardant, and self-cleaning fabrics via a simple dipping method. The prepared coated textile samples find numerous applications in various biomedical purposes and can also be used as a protecting material.
Lignin nanoparticles were synthesized using a high-shear homogenizer (Heidolph, Silentcrusher M) to prepare a 30% lignin nanoparticle dispersion in water for 5h to 20 h at a high speed ranging from 10000 rpm to 30000rpm.
MoS2 nanosheets are synthesized through sand grinding with the aid of tannic acid (TA). TA was first dispersed in water by mechanical stirring, then a fixed amount of MoS2 (3 phr) is added and allowed for mechanical stirring, followed by sand grinding.
MoS2/TA-Lignin hybrid dispersion is prepared by homogenization and sonication of lignin nanoparticles (LNP, 7 phr) and MoS2/TA dispersion (3 phr).
Nanofiller dispersions are mixed with natural rubber latex by probe sonication, and the NRL dispersion is coated on the fabric by dipping method.
Three types of NRL dispersion-coated fabrics are prepared:
• NRL/LNP dispersion coating followed by NRL/MoS2-TA to obtain LMC
• NRL/MoS2-TA coating followed by NRL/LNP to obtain MLC
• NRL containing MoS2/TA-Lignin hybrid dispersion to obtain MLM
For comparison, an NRL coated sample (NR) is also prepared. After dipping and drying, the samples are vulcanized.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated herein, and constitute a part of this disclosure, illustrate exemplary embodiments of the disclosed methods and systems in which like reference numerals refer to the same parts throughout the different drawings. Components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Some drawings may indicate the components using block diagrams and may not represent the internal circuitry of each component. It will be appreciated by those skilled in the art that disclosure of such drawings includes disclosure of electrical components, electronic components or circuitry commonly used to implement such components.
Fig. 1 depicts the schematic representation of coating process.
Fig 2 depicts the synthesis of MLT from MoS2-TA dispersion and LNP dispersion
Fig 3 depicts the FT-IR of Tannic Acid (TA), Lignin nanoparticles (LNP), MT and MLT
Fig 4 depicts the XRD patterns of MT, TA, LNP, and MLT
Fig 5 depicts the Raman spectrum of bulk MoS2 and hybrid nanomaterial
Fig 6 depicts the Optical microscopy images of a) bulk MoS2 b) and hybrid nanomaterial
Fig 7 depicts the FE-SEM images of MoS2 (a & c) and MLT (b &d) at 2μm and 500 nm
Fig 8 A) and Fig 8 B) depicts the TEM micrographs of MoS2 and MLT C) HR-TEM image of MLT
Fig 9 depicts the Optical microscopy images of base and coated textiles
Fig 10 depicts the FE-SEM images of the base fabric and coated textiles at 2μm
Fig 11 depicts the XRD diffraction peaks of pure and coated textiles
Fig 12 depicts the water absorption results of pure fabric and coated fabrics
Fig 13 depicts the water contact angle results of pure fabric and coated fabrics
Fig 14 depicts the Antibacterial results of cloth and coated samples
Fig 15 depicts the Viability of L929 cells upon interaction with uncoated and coated samples
Fig 16 depicts the Cell images of L929 after treatment with uncoated and coated samples
Fig 17 depicts the microscopic images obtained from the scratch wound-healing assay
Fig 18 depicts the self-cleaning test of uncoated and coated fabrics
Fig 19 depicts the images of Coffee stain on textiles.
Fig 20 depicts the Coffee stain on textiles before and after drying
Fig 21 depicts the tensile strength results of pure fabric and coated fabrics
Fig 22 depicts the images showcasing the acid resistance of uncoated and coated fabrics
Fig 23 depicts the horizontal flammability images of coated textiles
Fig 24 depicts the UV-visible transmittance spectra of coated fabrics
DETAILED DESCRIPTION OF THE INVENTION
Some embodiments of the present disclosure, illustrating all its features, will now be discussed in detail. It must also be noted that as used herein and in the appended claims, the singular forms "a", "an" and "the" include plural references unless the context clearly dictates otherwise.
Various modifications to the embodiment will be readily apparent to those skilled in the art and the generic principles herein may be applied to other embodiments. However, one of ordinary skill in the art will readily recognize that the present disclosure including the definitions listed here below are not intended to be limited to the embodiments illustrated but is to be accorded the widest scope consistent with the principles and features described herein.
A person of ordinary skill in the art will readily ascertain that the illustrated steps detailed in the figures and here below are set out to explain the exemplary embodiments shown, and it should be anticipated that ongoing technological development will change the manner in which particular functions are performed. These examples are presented herein for purposes of illustration, and not limitation. Further, the boundaries of the functional building blocks have been arbitrarily defined herein for the convenience of the description. Alternative boundaries can be defined so long as the specified functions and relationships thereof are appropriately performed. Alternatives (including equivalents, extensions, variations, deviations, etc., of those described herein) will be apparent to persons skilled in the relevant art(s) based on the teachings contained herein. Such alternatives fall within the scope and spirit of the disclosed embodiments.
Before discussing example, embodiments in more detail, it is to be noted that the drawings are to be regarded as being schematic representations and elements that are not necessarily shown to scale. Rather, the various elements are represented such that their function and general purpose becomes apparent to a person skilled in the art. Any connection or coupling between functional blocks, devices, components, or other physical or functional units shown in the drawings or described herein may also be implemented by an indirect connection or coupling. A coupling between components may also be established over a wireless connection. Functional blocks may be implemented in hardware, firmware, software or a combination thereof.
Further, the flowcharts provided herein, describe the operations as sequential processes. Many of the operations may be performed in parallel, concurrently or simultaneously. In addition, the order of operations maybe re-arranged. The processes may be terminated when their operations are completed but may also have additional steps not included in the figured. It should be noted, that in some alternative implementations, the functions/acts/ steps noted may occur out of the order noted in the figured. For example, two figures shown in succession may, in fact, be executed substantially concurrently, or may sometimes be executed in the reverse order, depending upon the functionality/acts involved.
Further, the terms first, second etc… may be used herein to describe various elements, components, regions, layers and/or sections, it should be understood that these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are used only to distinguish one element, component, region, layer or section from another region, layer, or a section. Thus, a first element, component, region layer, or section discussed below could be termed a second element, component, region, layer, or section without departing form the scope of the example embodiments.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which example embodiments belong. It will be further understood that terms, e.g., those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As used herein, the singular forms “a,” “an,” and “the,” are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, the terms “and/or” and “at least one of” include any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises,” “comprising,” “includes,” and/or “including,” when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Various embodiments of the invention provide a method of synthesizing coated textiles from natural rubber with lignin and molybdenum disulfide for biomedical and protective applications and a composition thereof. More particularly, the present invention describes insertion of various nanofillers into Natural Rubber Latex (NRL) which improves and introduces new properties to final natural rubber nanocomposites. The present invention discloses fabrication of biocompatible NR latex with Molybdenum disulfide (MoS2) nanosheets and lignin resulting in a coated textiles which provide unique properties to the textile. It makes the textile hydrophilic, antimicrobial, wound healing, acid resistance, UV blocking, flame retardant. Also, it incorporates the property of self-cleaning via a simple dipping method. The prepared coated textile is in great demand in various field of such as for biomedical purposes and as a protecting material.
One of the embodiment of the present invention is described in greater details, Kraft lignin and MoS2 (6 μm and 99 %) are acquired from Sigma Aldrich, while tannic acid (TA) is obtained from Dwarkesh Enterprise. A polyester-cotton blend having 70% polyester and 30% cotton is used as the base material. Water is used for the preparation of nanofiller dispersion. Double centrifuged latex (DRC-60%) is utilized for the preparation of prevulcanized latex.
In an embodiment, Lignin nanoparticle (LNP) was synthesized. A high-shear homogenizer is prepared with 30% lignin nanoparticle dispersion in water. The homogenization method was carried out for time duration ranging from 5h to 20h at a speed ranging from 10000 rpm to 30000rpm.
Exfoliation of MoS2 using Tannic acid (MT)
With the aid of TA, the synthesis of MoS2 nanosheets is accomplished through the process of sand grinding. Initially, tannic acid is dispersed in water by mechanical stirring, and a fixed amount of MoS2 (3phr) is added and allowed for 1h of mechanical stirring. After that, the dispersion is sand grinded for 1h.
Synthesis of MoS2/TA-Lignin hybrid (MLT) dispersion
MoS2/TA-Lignin hybrid dispersion is prepared by 1h homogenization and 1h sonication of LNP (7phr) and MoS2/TA dispersion (3phr).
Preparation of NRL-coated fabrics
Nanofiller dispersions are mixed with natural rubber latex by probe sonication, and the NRL dispersion is coated on the fabric by dipping method. Three types of NRL dispersion coated fabrics are prepared.
Initially, the fabric is coated with NRL/LNP dispersion. After drying, a second coating is done with NRL/MoS2-TA dispersion to obtain LMC. Similarly, the second sample is prepared by initial coating with NRL/MoS2-TA followed by a second coating with NRL/LNP to obtain MLC. Moreover, NRL containing MoS2/TA-Lignin hybrid dispersion is also prepared to obtain MLM. For comparison, NRL coated sample is also prepared (NR). After dipping and drying, the samples are vulcanized at 100°C for 1h. Fig 1 discloses the schematic illustration of coating. Accordingly:
• MLM- Polycotton textile coated by NRL/MLT
• LMC- Polycotton textile coated by NRL/LNP dispersion followed by NRL/MoS2-TA
• MLC- Polycotton textile coated by NRL/MoS2-TA dispersion followed by NRL/LNP
Characterization of MoS2-/TA-Lignin hybrid and Coated textiles
Various analytical methods characterized the hybrid nanomaterial and coated fabrics. Fourier transform infrared (FT-IR) spectroscopy is conducted using a spectrometer between 400 cm-1 to 4000 cm-1. The crystalline and amorphous nature of the nanomaterial and fabrics are studied through X-ray diffraction (XRD) with the Bruker D8 Advance instrument (0 to 900, Cu Kα and 1.54 nm). Raman analysis is performed with the Confocal Raman Microscope, alpha 300 A, Witec Inc. The morphology of the nanofiller and coated materials is examined using the Zeiss Sigma field emission scanning electron microscope (FESEM). Using Jeol/JEM 2100 high-resolution transmission electron microscopy (HRTEM), a detailed structural analysis of the nanomaterials is conducted.
Olympus CX41 instrument recorded the optical microscopy images of coated samples with 4x magnification. An atomic force microscope (Alpha300RA AFM & RAMAN, WITec GmbH, Ulm, Germany) is utilized for the analysis of surface roughness.
The mechanical properties of the textiles with a rectangle shape are made according to ASTM D 412-06a Standard and tested using UTM (Instron 5984, Instron, USA). The wettability of the textiles is studied by recording the contact angle with a contact angle goniometer and the profile of water on the solid material is captured by an optical subsystem. The system consists of high-resolution cameras and software to capture and analyze the CA. To test the self-cleaning activity of clothes, turmeric powder was put onto the clothes to create an artificially contaminated surface. The air permeability of the samples is tested using a pressure of 125Pa, according to ASTM D737. A horizontal flame resistance is done on coated and uncoated fabrics using flame from a gas burner. UV and visible light-blocking properties of the fabrics are confirmed using the analysis by UV-1700 Spectrometer in transmittance mode.
Acid resistance
The acid resistance of the samples is evaluated by immersing 2 cm × 2 cm samples into a concentrated sulfuric acid-containing petri dish at room temperature. The physical changes are evaluated, and images are captured.
Water absorption Test
For the water absorption test, samples are dried, and initial weight is measured. After
that, the specimens are immersed in a glass bottle containing water and kept at 23°C for 24 hours. Sample weights are recorded in specific time intervals.
Water Absorption% = Weight after immersion − Weight before immersion
______________________________________________
Weight before immersion× 100
Antibacterial Test
The bactericidal activity of coated fabrics is examined using the agar well diffusion technique on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus).
A
pproximately 15-20 mL of Mueller-Hinton agar (MHA) is dispensed onto Petri dishes and permitted to solidify. Subsequently, an inoculum of both bacteria is spread uniformly on the Petri dishes, and test samples (1cm2) are placed on the surface of the MHA plates.
The plates are then incubated for 24 hours at 36ºC ± 1ºC, under aerobic conditions.
Following incubation, the zone of microbial growth inhibition is measured.
Cytotoxicity
Cytotoxicity studies are also conducted against the L929 using the MTT assay. Each test samples is cut into three different pieces of equal sizes (3.5 mm × 3.5 mm) and subjected to sterilization using UV irradiation. Following sterilization, each piece is placed into individual wells of a sterile cell-culture grade 96-well plate, with wells without samples serving as control. Following treatment with the textile samples, the plates underwent an additional 24-hour incubation. Subsequently, the media from the wells are aspirated and discarded, and MTT solution in phosphate buffered saline is introduced into the wells.
Formazan crystals formed during an additional 2-hour incubation. The supernatant is then extracted, and dimethylsulfoxide is introduced into each well. Using a microplate reader, the absorbance at 570 nm was recorded.
The cell viability can be determined using the following equation:
Scratch wound healing assay
The samples (2 cm2) are placed in 6 well plates containing cultured L929 cells. A straight line ‘‘scratch’’ is created on the cell monolayer using a pipette tip. Debris is cleared, and the scratch’s edge is smoothened by washing the cells once with the growth medium, followed by replacement with fresh medium. The well plate underwent incubation in a tissue culture incubator at 370C. Photomicrographs were captured at different time points (0 h, 12 h, 24 h and 36 h). The plates were periodically removed from the incubator, examined periodically, examined, and images are taken using a phase-contrast microscope before being returned to resume incubation.
Results and Discussion
MoS2/TA-Lignin hybrid
Lignin is a heterogeneous complex biopolymer that contains many functional groups which include aliphatic and phenolic hydroxyl groups, methoxy, carbonyl, carboxylic acid, ketone, and quinone groups. Tannic acid is also a biomaterial having plenty of hydroxyl groups in its structure. Here, MoS2 and lignin are selected as nanofillers for NR, whereas tannic acid served as the exfoliating agent for MoS2. In MT dispersion, MoS2 is in the exfoliated stage due to the action of shearing force and centrifugal motion during the sand grinding, and tannate ion was adsorbed on the MoS2 surface and some of its hydroxyl functional groups are free.
Moreover, excess tannate ions also existed in the MT dispersion. The addition of LNP into MT dispersion under homogenization allows the mixing of LNP in the MT dispersion.
During the homogenization, functional groups on LNP may react with TA on the MoS2 nanosheet surface and excess tannate in the dispersion. Further thinning and fragmentation of the already exfoliated few layers of MoS2 takes place during the sonication. Fig 2 shows the schematic illustration of MLT synthesis.
FT-IR
FT-IR spectra of all the samples exhibit complexicity attributed to the diverse functional groups present on the biopolymer as shown in Figure 3. LNP shows a broad peak within the 3700-3000cm-1 range from the O-H groups in aliphatic and phenolic structures. C-H stretching of methylene or methyl group at 2941 and C=O stretching around 1700-1600 cm-1. The peaks observed at 1507 cm-1, 1467 cm-1, and 1420 cm-1 are assigned to C-C aromatic skeletal stretching, C-H aromatic skeletal stretching, and CH vibration in the methyl group, respectively. The stretching of C-O in the aromatic ester was noted at 1262, 1218 and 1124 cm-1. The hydroxyl group in tannic acid is detected within the range of 3600-3100 cm-1. Peaks at 2922, 1650 and 1355 are because of the C-H stretching vibrations, vibrating of aromatic of C=O and C–O stretching vibrations, respectively. Peaks associated with O–H and C–O are situated at 1415 and 1237, respectively. Bending of aromatic C−H bonds observed at 757. MT samples exhibited all the peaks of tannic acid with minor reduction in peak intencities which indicates the sufficient functionalization of tannic on MoS2 nanosheets. Peaks present on TA and LNP appeared in the MLT, which confirms the successful adsorption of TA and LNP on the MoS2 surface. Compared to MT, intensity TA peaks were reduced along with new peaks came from the LNP. Compared to MT, –OH peaks of MLT became wider and showed a slight shift proving the hydrogen bonding interaction between TA on MoS2 and excess tannic acid in the MoS2 dispersion with LNP.
Figure 4 represents the XRD analysis data of TA, LNP, MT and MLT. XRD is a powerful tool for the confirmation of MoS2 exfoliation. The observed diffraction peaks for MT at 2Ѳ of 14.31°, 32.39°, 39.44°, 50°, and 58.15° are indicative of the crystallographic planes (002), (100), (103), (105) and (110) planes, respectively, of the hexagonal MoS2.Moreover, a broad peak is evident at 18-25°, corresponding to tannic acid. MLT also showed the same XRD patterns as MT but a significant difference in intensity. The MLT peaks, particularly (002) peak, showed a reduction in intensity. This reduction is likely attributed to the destruction of the organized arrangement in MoS2, resulting from a higher degree of exfoliation, confirming that bulk MoS2 undergoes a transition to a few-layer structure.
Reduction in intensity of (002) peak is an identification of reduced layer number in MoS2. The exfoliation process led to a reduction in microcrystalline thickness, resulting in a decreased probability of meeting the Bragg′s condition for the planes in MoS2. Also, the amorphous peak is much broader than the MT due to the additional effect from the LNP.
Thus, it can be concluded that MLT consists of few layered materials. The presence of both tannic acids connected LNP on the MoS2 surface and excess TA-LNP connected system in the dispersions significantly reduces the restacking tendency of exfoliated MoS2 nanosheets.
Raman Analysis
The Raman analysis result of bulk MoS2 and hybrid nanomaterial are illustrated in Figure 5. Bulk MoS2 displays two peaks at 408.11 cm-1 and 378.45 cm−1 due to the out-of-plane vibrations (A1g) of sulphur and in-plane vibration (E12g) of molybdenum atoms, respectively.
Usually, as a result of the insertion of external agents, these two modes undergo some shifts, which are the blue shift for E1 2g and the red shift for A 1g. In this case, red shift is observed for A1g due to the decreased van der Waals forces; however, a shift in E1 2g is not detectable due to the lower intensity. Adsorption of polymer materials on the MoS2 and WS2 nanosheets surface does not cause any shift to the E1 2g. After the exfoliation, the intensity of both the bands is reduced because the reduced thickness and size of MoS2 caused less number of MoS2 for Raman scattering. Moreover, defects formed after the exfoliation on the edges or numerous functional groups from both the tannic acid and LNP also caused a reduction in intensity.
Morphological Analysis
Microscopic tests are carried out for the confirmation regarding the exfoliation process. Morphological studies of the hybrid are investigated initially by optical microscopy and obtained images are shown in Figure 6. From the images, it is clear that bulk MoS2 is in non-uniform and agglomerated form. However, MLT dispersion displays a more homogeneous dispersion without any agglomeration.
Morphologies of MoS2 and MLT samples are examined using FE-SEM. Pure MoS2 exhibited a structure consisting of many stacked layers, forming an agglomerated structure consistent with the optical images as shown in Figure 7a. Following the sand grinding, which is performed for 1-2 hours and homogenization, the originally stacked MoS2 layers underwent delamination, resulting in MoS2 nanosheets with irregular size. The size of MoS2 is reduced in MLT and the interlayer distance between MoS2 layers was increased due to the presence of TA and LNP as shown in Figure 7b.
A detailed examination of MoS2 at high magnification revealed a layer-by-layer stacked form in bulk MoS2 as shown Figure 7c whereas both TA and LNP are decorated on the surface as well as edges of MoS2 nanosheets as shown in Figure 7d.
Figure 8 shows TEM and HR-TEM images of both the pristine MoS2 and MLT samples. In Figure 8A, bulk MoS2 exhibits an aggregated structure, whereas Figure 8B indicates that the MLT has a nanosheet-like morphology. The MoS2 nanosheets are shown a random stacked arrangement and possess a transparent appearance, proving the thin nature of the prepared MoS2 nanosheets. SAED patterns of the MLT are also shown as inset, clear diffraction spots that confirm the existence of a few layers of MoS2 nanosheets. The high-resolution TEM image of the MLT sample as shown in Figure 8C, confirms the presence of TA and lignin in MoS2, which promotes the exfoliation of MoS2 into a few or monolayer nanosheets. The TEM images align well with the findings from XRD and Raman analysis.
NR-Lignin/MoS2 Textiles
Morphological Studies
Figure 9 depicts the optical microscopy images of both the base fabric and the coated fabrics. Images depict the extent of latex coating on the fabric. Colour of the pure CL is changed during the coating process, showing a successful coating of polymer coating on the textile surface. Base fabric shows more spaces in its image, whereas the spaces are reduced when the fabric is coated with NRL. Compared to NR, these spaces are fewer in LMC; however, the coating is not uniform. Coating with NR/MT on NR/LNP coating is very difficult. Coming to MLC, only a few spaces are visible. This might be due to the better initial coating with NR/MT. Compared to LMC, the second coating is better in MLC.
Surprisingly, no such small gaps are seen in MLM, which indicates the uniform dispersion of hybrid material over the fabric.
FESEM and the images analyzed surface morphology of pristine and coated textiles are shown in Figure 10. Before surface coating, the surface of the base fabric is smoother, and there is no inter-fiber adhesion between each fiber. However, some morphological changes occurred after coating with the latex dispersions. Tian et al. also reported the absence of surface original morphology of the cotton fabric by coating with chitosan and graphene oxide. The fabric surface is enveloped by the NRL covering (NR sample); resulting in the interconnection of fibres. Non-uniform dispersion of the second NR/MoS2 coating above NR/LNP coating is seen in the case of LMC, MoS2-TA remains agglomerated in some spaces. Dispersion of NR/LNP in MLC is better on NR/MoS2 coating when compared to LMC. A uniform dispersion and interconnection of nanofillers can be observed in MLM.
XRD patterns of original and latex-coated fabrics are illustrated in Figure 11. Recorded XRD patterns indicate that pure fabric shows three typical peaks at 17.3°, 22.4° and 26.2°. Natural rubber is amorphous. Thus, it does not give any strong peaks in XRD analysis, but it will give a strong, broad band at 18°. In the NR sample, peaks at 17.3° and 22.4° of pure cotton are shielded by the broad peak of natural rubber at 18°. In addition to this amorphous peak, some new diffraction peaks appeared for LMC, MLC, and MLM from the MoS2. In comparison to pure MoS2, all the peak intensity is reduced, affirming the presence of an intercalated or exfoliated structure. The intensity of all peaks in MLM is highly reduced due to the complete exfoliation of MoS2 due to the presence of TA, LNP, and NR, and the formation of an exfoliated structure can be easily substantiated. The peak intensity in LMC is also reduced, but this is due to the insufficient loading of MoS2 above the NR/LNP coating due to the non-uniform second coating. Compared to MLM and LMC, the intensity of all the peaks in MLC is higher, because of the formation of intercalated structure instead of exfoliated structure.
Water Absorption
Figure 12 shows the water absorption test results of the reference fabric and the coated fabrics at room temperature. Pure fabric is a blend of polyester and cotton. Thus, it shows the properties of both materials. The water absorption of polyester material is much less, but the presence of cotton reduces its water resistance properties. From the graph, it is observed that water absorption of control fabric is increased with an increase in time and reaches up to 73% due to the capillary action of cotton fibre. Here, the fibre surface is in direct contact with the water, allowing easy water absorption. However, the water absorption ability of NR-coated samples is much less than all samples. Because NR is inherently hydrophobic in nature, the coating of NRL over the fabrics forms a water-resistant coating resulting in a reduction in water absorption. Both LNP and MoS2-TA have hydrophilic properties and show better affinity for water. Thus, the insertion of LNP and MoS2-TA into NRL as part of a coating introduces some hydrophilic sites, thereby showing water absorption characteristics than NR.
Compared to LMC and MLC, MLM samples showed higher water resistance due to the hybrid structure formed by the reaction of tannic acid and lignin.
Contact Angle
To understand the interaction of the fluid with textiles and the hydrophobic or hydrophilic nature of fabrics, contact angle measurements were taken. Figure 13 displays the contact angle measurements of the fabrics. Pure fabric is hydrophobic due to the higher amount of polyester content. However, after some time, the water got spread over due to cotton content.
LMC, MLC, and MLM samples have lower contact angles, confirming their hydrophilicity. Due to this lower contact angle, these coated samples are ideal for biomedical purposes because the contact angle in the 40-85 range is suitable for cell adhesion and protein adsorption. The reduction in contact angle might be attributed to hydrogen bonding interactions involving water molecules and the plethora of OH groups from both lignin and tannic acid. However, the contact angle of MLM samples is higher than that of LMC and MLC, possibly because of a diminished number of hydroxyl groups in MLM samples, as tannic acid OH and lignin functional groups may undergo chemical interactions. Thus, it can be concluded that hydrophilic latex-coated fabrics can be used as antibacterial clothing.
Antibacterial Properties
The bactericidal efficiency of the coated samples is assessed to evaluate their ability to prevent microbes. Figure 14 represents the antibacterial action of coated textiles on both E.coli and S.aureus. The pure cloth exhibits no inhibition against both the organisms, however, natural rubber latex-coated samples exhibit a small inhibition zone, and this may be due to the zinc oxide present in the compounding recipe and bactericidal action of proteins in NRL. In comparison to CL and NR, the coated samples showed excellent bactericidal action, which might be due to the tannic acid and lignin present on the fabrics. Because these components are well-known antibacterial agents and can effectively hinder bacterial growth. Moreover, the antibacterial affect is further enhanced by the involvement of MoS2 nanosheets, because MoS2 nanosheets are also an excellent antibacterial agent.
MoS2 nanosheets sharp edges can cause physical damage to the bacterial cell wall upon direct contact. This damage may lead to the outflow of intracellular components and ultimately result in bacterial death.
Cytotoxicity Studies
Cytotoxicity studies results are depicted in Figure 15. The results demonstrate that uncoated cloth did not exert any cytotoxicity on the tested cell lines. However, cell viability is reduced by the coating on the cloth with NRL alone. Loss in the cell viability is recovered by the introduction of lignin NPs and MoS2-TA nanosheets into the NRL. Insertion of nanofillers into the NRL did not produce any toxicity to the cell lines and it helps to improve the biocompatibility of NRL. Phase contrast microscopy images of cells after 24h culture are included in Figure 16 which is consistent with the quantitative results. The images clearly show that there is no change in the morphology of the cells in the case of nanofillers containing NRL-coated samples (MLM, LMC, and MLC), however, morphology is changed in the case of NR sample.
Scratch wound healing
The cell migration ability of L929 cells is analyzed through in an vitro wound-healing assay in the presence of coated textiles (LMC, MLC, and MLM) and the obtained results are illustrated in Figure 17. As shown in the Figure, all the coated samples exhibited improved cell migration after 36 h compared to the control, proving that the cells were capable of migrating, proliferating, and filling gaps with increasing time. Cell migration was highest in the case of the MLC sample. Improved cell migration is due to the synergistic effect of MoS2 nanosheets, tannic acid, and lignin
Self-Cleaning
Self-cleaning ability is a highly useful property of coated textiles for its practical applications, and self-cleaning tests are performed on the pristine and coated fabrics. Turmeric powder is used as artificial dust and placed on the samples at an angle of around 15 as shown in Figure 18. The pristine fabric is completely wetted and polluted due to the cotton content in the fabrics. When the water droplet interacts with dirt, it completely sticks to the surface, and there is no further movement, leaving the surface dirty. However, coated fabrics show excellent self-cleaning ability. When water is released from the top of the surface, the water droplets collected the dust particles, leaving a clean surface for MLM, MLC, and LMC. For NR, only trace amounts of particles are left on the surface.
Stain Removal
Stain from food, drinks, blood, dye, etc., is another major issue in the textile industry. Stains can be removed from clothes, but some spots may remain on the cloth. Therefore, stain removal is very risky in maintaining its original texture. Stain removal is also examined, and the results are shown in Figure 19. The stain removal performance of the samples is tested by the degree of removal of the coffee stain. Figure 19 shows the images of coffee drops on the uncoated and coated textile. Coffee drops were spread completely in the case of pure fabrics. The stain was also not completely removed after washing. For coated samples, the coffee drops stuck over the surface without any penetration to the inner surfaces and were easily removed by washing with water. Images of stained fabrics before, after, and after washing are illustrated in Figure 20. The coffee stain on the original cloth spread completely over the cloth and was not completely removed after washing. However, the stains stayed on the sample surfaces for a long time without any absorption and were removed easily from the coated samples after drying. For NR, some minute marks were retained after washing. However, after washing, LMC, MLC, and MLM retained their original surface texture. This proves the easy stain removal of the coated textiles, which opens the scope of using it as the middle layer of reusable pads. It can also be used for wound dressing applications where the medicine stays in contact with the
wound longer.
Mechanical Properties
Figure 21 displays the tensile strength results of the textiles. The tensile strength of pure fabric increased to about 18% after coating with NR latex. It is further increased upon MoS2 and lignin insertion. However, there is not much improvement in the case of LMC, which can be attributed to the non-uniform second coating. Surprisingly, a greater improvement in tensile strength can be observed in the case of MLM (53%). This might be coming from the hybrid structure formed by the MoS2 and lignin in NR latex, which can efficiently transfer the applied stress. Latex coating strongly adheres on the textile fiber and inhibits them from unraveling or coming loose. Latex coating develops a flexible and strong protective coating over the textile surface which prevents external damage and improves mechanical stability.
Acid Resistance
Most fabric materials have less tolerance to acids, especially concentrated acids. Damage to clothes by concentrated acids is one of the major threats during lab experiments. Acid resistance of the original fabric and coated fabrics is performed by immersing the samples in concentrated sulfuric acid in Petri dishes. As seen in Figure 22, pure fabric immediately undergoes deterioration in the acid solution and only a little remains after 30 min. Conversely, NR sample decomposition was much less than CL, but some physical changes occurred. MLM sample is more resistant to sulfuric acid than LMC and MLC even though they have a double coating, which illustrates the strength of the hybrid formed between the lignin and MoS2 through tannic acid. In 2023, Song et al demonstrated the synthesis of polyimide (PI) coated cotton with excellent acid resistance properties. Pure cotton material is completely broken down in concentrated hydrochloric acid, but the PI-coated materials exhibited a small shrinkage in the acid medium and maintained good fabric structure after the exposure period proving its ability to be used as protective clothing.
Flame Resistance
Textile materials are flammable and cannot be used for fire-related applications. The introduction of flame resistance to textile materials helps expand its applications in various fields. Upon exposure to direct flame, the pure cloth ignited quickly, and the fire spread faster and burned completely within 24s, and a small amount of residue remained as shown in Figure 23.
However, the flammability of coated materials exceeds 24s. Compared to NR and LMC, MLC and MLM exhibited better flame resistance properties. This may be due to the barrier effect of MoS2 and the flame resistance of tannic acid. MoS2 and TA were also present on LMC, but the amount is lesser than that of MLC and MLM due to the non-uniform dispersion of MoS2/TA latex dispersion over lignin latex dispersion. Compared to MLC, MLM showed better resistance to flame because of the hybrid structure that retard the flame more effectively. MLM is not completely burned within 24s as confirmed by its char residue.
UV blocking properties
Lignin materials have strong UV absorbance ability and thus can be considered excellent UV-blocking agents. Figure 24 shows the UV-visible light transmission spectra of plain fabric and coated textiles measured from 200-900 nm wavelengths. Polyester materials usually provide sufficient UV protection compared to pure cotton. However, in this case, the transmittance of the bare fabric is high compared to pure polyester due to the presence of cotton material. NRL-coated sample shows less transmittance than pure fabric. Surprisingly, all the lignin and MoS2 coating samples showed zero transmittance in the UV range, indicating the effective UV-blocking properties of LMC, MLC, and MLM samples.
Moreover, these samples can also block visible light, a characteristic that is likely attributed to the presence of MoS2. Lignin material is only specific to UV blocking: however, MoS2 can block UV and visible light. MLM samples completely block UV as well as visible light, attributed to the uniform coatings of latex dispersion on fabrics. LMC is less effective in blocking visible light compared to MLC and MLM, attributed to the uneven coating of NR/MoS2 over the NR/lignin coating. This excellent UV and visible light shielding is coming from the lignin and MoS2 materials and the filling of gaps between the yarns with these materials during the coating process.
This work demonstrated the fabrication of MoS2 and lignin-containing NR latex-coated textiles having multifunctionalities. Characterization of the fabricated latex-coated samples is done using optical microscopy, FE-SEM, and XRD. Detailed analysis of the coated textile samples confirmed that the fabricated samples are hydrophilic, antimicrobial, self-cleaning, biocompatible, wound healing, UV-blocking, acid-resistant, etc. The entire fabrication process is carried out using water as solvent and eco-friendly materials as additives, making the coating process follow a green pathway. It can be concluded that fabricated coated textiles exhibit multifunctional properties and exhibit utility in various applications. MLM samples are mechanically strong, acid resistant, and UV blocking which depicts its utilization in sun-protective and chemical-resistant protective clothing. However, LMC and MLC samples have biocompatibility and have greater antimicrobial and wound healing properties which enable its application as potential surgical textiles for medical purposes.
, C , Claims:WE CLAIM:
1. A method for preparing a coated fabric with enhanced properties, said method comprising the steps of:
• synthesizing lignin nanoparticles by homogenizing a lignin dispersion in water;
• exfoliating MoS2 by dispersing tannic acid (TA) in water via mechanical stirring, subsequently sand grinding the mixture to obtain exfoliated MoS2 nanosheets;
• preparing MoS2/TA-Lignin hybrid dispersion by homogenizing a lignin nanoparticle (LNP) dispersion with the exfoliated MoS2/TA dispersion, followed by sonicating the mixture to form a MoS2/TA-Lignin hybrid dispersion.
• coating fabric with NRL dispersion by mixing the MoS2/TA-Lignin hybrid dispersion and other nanofiller dispersions with natural rubber latex (NRL) using probe sonication and applying the NRL dispersion onto the fabric using a dipping method.
• creating multiple coatings to obtained different types of coated fabrics
• drying and vulcanizing the coated fabrics.
wherein said method provides a systematic approach for producing coated fabrics with improved characteristics through the incorporation of exfoliated MoS2 and lignin-based materials.
2. A method for preparing a coated fabric with enhanced properties as claimed in claim 1 wherein said lignin nanoparticle is obtained from 30% lignin nanoparticle dispersion in water.
3. A method for preparing a coated fabric with enhanced properties as claimed in claim 1 wherein said homogenization is carried out for time duration ranging from 5h to 20h at a speed ranging from 10000 rpm 30000rpm.
4. A method for preparing a coated fabric with enhanced properties, wherein said step of exfoliation is performed by adding a fixed amount of MoS2 to the TA dispersion while stirring for 1-2 hours.
5. A method for preparing a coated fabric with enhanced properties, wherein said sand grinding is performed for 1-2 hours.
6. A method for preparing a coated fabric with enhanced properties, wherein said homogenizing a lignin nanoparticle (LNP) dispersion with the exfoliated MoS2/TA dispersion is performed for 1-2 hour followed by sonicating the mixture for 1 hour.
7. A method for preparing a coated fabric with enhanced properties, wherein said different types of coated fabrics are as follows:
• Coating the fabric with NRL/LNP dispersion, drying, and applying a second coating with NRL/MoS2-TA dispersion to obtain LMC.
• Coating the fabric with NRL/MoS2-TA, drying, and applying a second coating with NRL/LNP to obtain MLC.
• Coating the fabric with NRL containing MoS2/TA-Lignin hybrid dispersion to obtain MLM.
8. A method for preparing a coated fabric with enhanced properties, wherein said vulcanization is performed in the range of 100°C- 150°C for 1 hour.
9. A method for preparing a coated fabric with enhanced properties, wherein said method resulted in coated fabrics which are hydrophilic, antibacterial, self-cleaning, wound healing, UV-blocking latex-coated textiles containing lignin and MoS2 through a green method.
| # | Name | Date |
|---|---|---|
| 1 | 202441072936-STATEMENT OF UNDERTAKING (FORM 3) [26-09-2024(online)].pdf | 2024-09-26 |
| 2 | 202441072936-REQUEST FOR EXAMINATION (FORM-18) [26-09-2024(online)].pdf | 2024-09-26 |
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| 8 | 202441072936-FIGURE OF ABSTRACT [26-09-2024(online)].pdf | 2024-09-26 |
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| 13 | 202441072936-DECLARATION OF INVENTORSHIP (FORM 5) [26-09-2024(online)].pdf | 2024-09-26 |
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| 15 | 202441072936-Proof of Right [23-12-2024(online)].pdf | 2024-12-23 |
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| 18 | 202441072936-ENDORSEMENT BY INVENTORS [23-12-2024(online)].pdf | 2024-12-23 |