WO2022190071A1

WO2022190071A1 - Synthesis and fabrication of zinc oxide copper oxide composite nanofibers with antimicrobial properties and the ability to coat various fabrics

Info

Publication number: WO2022190071A1
Application number: PCT/IB2022/052231
Authority: WO
Inventors: Hamidreza REZAEIAN MEHR; Parisa AFSARI
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-03-10
Filing date: 2022-03-12
Publication date: 2022-09-15
Anticipated expiration: 2023-09-10

Abstract

The process of synthesis and production of zinc oxide-copper oxide composite nanofibers with AZnO-BCuxO formulation (A = 0.95, B = 0.05, X = 1,2) with the ability to coat all types of fabrics with antimicrobial properties. In this project, the precursors of zinc acetate, copper acetate were used as the main suppliers of zinc oxide and copper oxide, respectively; ethanol was used as the solvent, and polyvinylpyrrolidone was the fiber-forming polymer for synthesis. the production of hollow composite nanofiber ZC5 with the Chemical formulation AZnO-BCuxO (A = 0.95, B = 0.05, X = 1,2) has anti-coronavirus (n-SARS-CoV2 virus) properties with an efficiency of >99% and the production of anti-coronavirus fabric by airless jet spray method and hot press (simultaneously) with the efficacy of >99% against coronavirus.

Description

SYNTHESIS AND FABRICATION OF ZINC OXIDE COPPER OXIDE COMPOSITE NANOFIBERS WITH ANTIMICROBIAL PROPERTIES AND THE ABILITY TO COAT VARIOUS FABRICS fabrics

[0001] The process of synthesis and production of zinc oxide-copper oxide composite nanofibers with AZ no-bc u xo formulation (A = 0.95, B = 0.05, X =

1 ,2) with the ability to coat all types of fabrics with antimicrobial properties. In this project, the precursors of zinc acetate, copper acetate were used as the main suppliers of zinc oxide and copper oxide, respectively; ethanol was used as the solvent, and polyvinylpyrrolidone was the fiber-forming polymer for synthesis the production of hollow composite nanofiber ZC5 with the Chemical formulation AZnO-BCuxO (A = 0.95, B = 0.05, X = 1 ,2) has anti- coronavirus (n-SARS-CoV2 virus) properties with an efficiency of >99% and the production of anti-coronavirus fabric by airless jet spray method and hot press (simultaneously) with the efficacy of >99% against coronavirus.

Technical field

[0002] by electrospinning (D04H 1 -728) - for the spine, e.g., vertebrae, spinal discs (A61F 2-44)

Background Art

[0003] Synthesis of electro spun ZnO-CuO nanocomposite fibers and their dielectric and non-linear optic studies, Journal of Alloys and Compounds 507 (2010) 225-229

[0004] The blend of sol-gel processing and electrospinning technique, yields composite nanofibers of poly (vinyl alcohol) (PVA)-zinc acetate-copper acetate. Calcining these fibers resulted in nanocomposite fibers of ZnO-CuO with diameters of 50-100 nm which was revealed by the scanning electron microscope images Preparation of PVA-copper acetate-zinc acetate composite sol 1.2 g of copper acetate was dissolved in 10 mL of deionized water and added to 30 g aqueous PVA solution (about 10 wt%) with constant stirring at 60 _°C for 1 h. 10 mL of deionized water was added to 1.2 g of zinc acetate and then slowly added into the already prepared copper acetate- PVA solution. To this solution 6 mL of ethanol and 0.5 mL acetic acid were added while stirring. Acetic acid prevents precipitation and acts as hydrolysis- condensation catalyst. The above prepared solution was stirred for 6 h keeping in a water bath maintained at 50 _°C. A viscous.

[0005] In our design, hollow composite nanofibers with a unique formulation (az n O - be u xo = 1.2, A = 0.95, B = 0.05, X were synthesized by electrification by synthesizing a combination of CuO and CU20 in the composite composition under the calcination process. In addition, PVP polymer has been used as a polymer component for electrospinning. Innovative corona anti-virus properties according to ISO 18184 standard with more than 99% performance compared to control sample and antibacterial properties according to AATCC100 standard with a yield of more than 99% for non-woven textiles coated with these nanocomposites, it has been obtained by airless jet spray method and hot press (simultaneously).

[0006] Batch Preparation of CuO-ZnO-Loaded Nanofiber Membranes for Photocatalytic Degradation of Organic Dyes, Langmuir 2020, 36, 47, 14189— 14202

[0007] Composite nanofiber membranes (CNFMs) loaded with CuO-ZnO (CZCNFMs) have important applications in a series of organic and industrial catalytic reactions because of Nano effects of the nanofibers and the peculiar performances of semiconductor oxides. In this work, CZCNFMs with different mass ratios of Cu to Zn were successfully fabricated in batches using modified bubble electrospinning (MBE), a heat treatment method, and a hydrothermal method. The influences of the mass ratio of Cu to Zn on the morphologies, structures, and properties of the CNFMs were studied, and the obtained CNFMs with different mass ratios of Cu to Zn were applied to the photo degradation of methyl orange (MO) and methylene blue (MB). The results showed that when the mass ratio of Cu to Zn was 5:5, the fabricated CNFM had better morphology, structure, and mechanical properties and had the best degradation effects on MO and MB. In addition, the principal active substances produced during the photo degradation of MO were defined by free radical capture experiments, and the influences of the pH value of the MO solution on the photocatalytic activity of the CNFMs with the optimal mass ratio of 5:5 were discussed.

[0008] In our design, hollow composite nanofibers with a unique formulation (az n O - be u XO = 1.2, A = 0.95, B = 0.05, X were synthesized by electrification by synthesizing a combination of CuO and CU20 in the composite composition under the calcination process. As this unique combination has corona anti-virus and antibacterial properties simultaneously. As mentioned in the paper, only divalent zinc oxide and divalent copper oxide nanofibers have been synthesized. Also, the final application of our design is the preparation of non-woven spun bond fabric with anti-corona and anti bacterial properties simultaneously and its use in the preparation of masks with anti-corona and anti-bacterial media as well as air filters with the same property. However, in the mentioned article, the photocatalytic properties in the elimination of organic inks as external sources of water pollution have been studied. According to the antiviral and antibacterial results of our design, the synthesized hollow nanofibers not only use the photocatalytic mechanism to produce free radicals, but also have corona and antibacterial properties in environments without visible light spectrum.

[0009] Ultrasonic Coating of Textiles by Antibacterial and Antibiofilm Nanoparticles, Handbook of Ultrasonic and Sonochemistry pp 1 -27, 2106

[0010] The second section of the chapter explains the mechanism of the ultrasound-assisted deposition of nanoparticles on textile. The coating can be performed by an in situ process where the nanoparticles are formed and immediately thrown to the surface of the fabrics. This approach was used for ZnO, CuO, and Zn-CuO nanoparticles. In addition, the sonochemical process can be used as a “throwing stone” technique, namely, previously commercially synthesized nanoparticles will be placed in the sonication bath and sonicated in the presence of the fabric. The last achievements in the antimicrobial finishing of textile with metal Nano-oxides by sonochemical method are provided in the third section. One of the proofs that the sonochemical method is one of the best coating methods is that the sonochemically coated fabrics were washed 65 cycles in hospital washing machines (75 or 92 °C) and have shown excellent antibacterial properties at the end of the process.

[0011] Efficient adsorption and antibacterial properties of electrospun CuO- ZnO composite nanofibers for water remediation, 2016, Journal of Hazardous Material 321

[0012] On the face of impending global water resources, developing low-cost and efficient water treatment technologies and materials thereof is highly important. Herein, we explore the adsorption capacity and antibacterial properties of CuO-ZnO (CZ) composite nanofibers. The ultrafine nanofibers were fabricated using simple and inexpensive electrospinning technique and were further characterized using Field Emission-Scanning Electron Microscope (FESEM), Transmission electron microscope (TEM) and X-Ray Diffraction (XRD), Thermogravimetry analysis (TGA), Fourier transform Infrared Spectroscopy (FTIR).

[0013] Sonochemical coating of textiles with metal oxide nanoparticles for antimicrobial fabrics, US93159377B2

[0014] We disclose a system for preparing antimicrobial fabrics, coated with metal oxide nanoparticles by means of a novel sonochemical method. These antibacterial fabrics are widely used for production of outdoor clothes, under wear, bed-linen, bandages, etc. The deposition of metal oxides known to possess antimicrobial activity, namely ZnO, MgO and CuO, can significantly extent the applications of textile fabrics and prolong the period of their use. By means of the novel sonochemical method disclosed here, uniform deposition of metal oxide nanoparticles is achieved simply.

[0015] In this invention, woven linen fabric is used for covering, while in our design, non-woven spunbond fabric is used. In this invention, the focus is on the antibacterial properties of the final fabric, while in our design, the focus is on the corona anti-virus property with a performance of more than 99% covered by non-woven fabric.

[0016] Nanofiber allergen barrier fabric

[0017] United States Patent Application 20080120783

[0018] An allergen-barrier fabric comprising at least one porous layer of polymeric nanofibers, a fabric layer super jet and adhered to the nanofiber layer, and optionally a fabric layer subjacent and adhered to the nanofiber layer, wherein the superjacent and optional subjacent fabric layers are adhered to said nanofiber layer such that the allergen-barrier fabric has a mean flow pore size of between about 0.01 pm and about 10 pm, and a Frazier air permeability of at least about 1.5 m3-min-m2.

Summary of invention

[0019] In this section, the steps of synthesizing zinc oxide and copper oxide composite nanofibers are briefly described: After preparing the raw materials, the initial solution for the synthesis of nanofibers was prepared, which included weighing the raw materials, adding them to ethanol, and stirring for 3 h to create a homogeneous solution. Then, the solution was transferred into the syringe to reach the fibrous form by the device. Finally, after drying and calcination, hollow nanofibers were formed.

Technical problem

[0020] Nano fabrics is an emerging and interesting application of nanotechnology, which involves dealing with nanofibers at the atomic and molecular levels to tweak their properties. The increasing demand for sophisticated fabrics with special features and exceptional comfort drives the need for the use of nanotechnology in this industry. Scanning Electron Microscope (SEM) as a magnifying device that uses electrons instead of light, is used in nanotechnology. It uses electron bombardment to create images of objects as small as 10 nanometers. The construction of the SEM has allowed researchers to study larger samples more simply and clearly. The sample bombardment causes electrons to be released from the sample to the positively charged surface, and convert to signals. The movement of the beam on the sample provides a set of signals and causes the microscope to displays an image of the sample surface on the computer screen. The obtained fiber samples are dried and then examined by an SEM microscope. Figure 4 shows the uniform structure of zinc oxide hollow nanofibers and zinc oxide-copper oxide composites with different compositions before and after calcination. Thermal analysis is the measurement of the change that occurs in the physical properties of a material when the temperature is changed according to a special program. Physical properties refer to quantities such as weight, geometric size, heat capacity, electrical conductivity, etc. that change with increasing the sample temperature. A thermal program means heating the sample according to a special temperature program and in a specific environment. Thermogravimetry (TG) and differential thermal analysis (DTA) is thermal analysis methods that are based on measuring the weight of the sample during heating and measuring the temperature difference between the unknown and control samples, respectively.

[0021 ] In this study, TG and DTA were performed to investigate the thermal behavior of the synthesized fibers at the temperature range of room temperature up to 600 °C, air environment, and heating rate of 5 °C-min. As shown in the TG diagram, during the calcination process at up to 600 °C, 95% of the sample weight has gradually reduced in several stages. This gradual reduction at 50-100 °C is related to the evaporation of water absorbed in the solvent and acetate groups. Weight loss of about 45% at 170-270 °C is related to the chemical decomposition of metal salts (zinc acetate and copper acetate) and the formation of metal oxide structures in composite nanofibers. At 410-580 °C, weight loss of about 40% is observed in the sample, which indicates the chemical decomposition of PVP. The lack of significant weight loss observed at >450 °C indicates the completion of the PVP decomposition process. The absence of changes at >565 °C indicates the completion of the calcination process and the formation of zinc oxide-copper oxide nanocomposite crystals. ABB, Bomem, MB 100 spectrometer was used to evaluate the samples using infrared spectroscopy. To do this, first, the tablets were made from potassium chloride as the reference material, as well as from the powder sample, and then irradiated with light. For each sample, the light transmission spectrum was measured at 400-4000 cm ¹, and qualitative data were obtained from the bond vibrations in the powders. In the study of bonds in fibers before calcination by infrared spectroscopy, absorption bonds at 3130-3454 cm ¹ indicated the adsorbed tensile bond of O-H on the surface of the fibers. Adsorbent bonds at 2923.88, 2954.74, 1674.10, and 1425.30- 1461.94 cm ¹ indicate symmetric and asymmetric tensile bond of CH in -CH2 groups, pyrrolidone ring, C = O bond, and C-N tensile bond, respectively. Moreover, the absorption at 1288.36, 730.97, as well as 648-.4 & 574.75 cm^-1 are related to the tensile bond of (-C) in the CH2- group, C-C bond, and N- C=0 bond, respectively. All wavelengths of these adsorption bonds are related to PVP as the raw material.

[0022] Considering the use of paraffin as the core of primary fibers, the wavelength of 730.97 cm ¹ can be related to the (C-C) bond of the paraffin hydrocarbon chain. The absorptions at 1375.27 and 2854.45-2954.74 cm-1 indicate the flexural (C-H) and tensile (C-H) bonds of paraffin, respectively.

[0023] According to the infrared spectrum shown in Figure 5, all peaks related to PVP and paraffin have disappeared and new peaks have emerged at 449.38 and 505.01 cm ¹, which are related to the tensile bond of Zn-0 in zinc oxide and Cu-0 in copper oxide, respectively, indicating the formation of zinc oxide and copper oxide following the calcination process. In addition, the peaks at 3454.27 and 1361.67 cm ¹, respectively indicate the tensile and flexural bonds of O-H in the moisture absorbed on the surface of the fibers. The absorption peak at 2923.88 cnv¹ is related to the C-H bond that remained from the primary fibers in a very small amount.

Solution of problem

[0024] Synthesis is a chemical reaction that is designed to provide a pure product with the desired efficiency to solve previous problems and optimize them. Moreover, the design of these reactions should be such that they have no operational complexity. There are several methods for producing materials and reaching the final material. Even the basic methods are used in some cases. For these methods to be useful, they must be highly efficient and suitable for a wide range of materials. Among the applications of nanomaterials used in this project are their antibacterial and antiseptic properties because they are in direct contact with microbes. These nanomaterials are used as antiviral, antifungal, and antibacterial agents when added to the solution. Copper nanoparticles are also widely used in this new science and have many applications in various fields. Zinc oxide is a nanoparticle with unique properties. It is considered one of the richest nanostructures due to its suitable physicochemical properties. Among the special properties of ZnO nanoparticles are the high chemical stability and, most importantly, the antibacterial properties. [0025] In this section, the steps of synthesizing zinc oxide and copper oxide composite nanofibers are briefly described: After preparing the raw materials, the initial solution for the synthesis of nanofibers was prepared (Figure 1), which included weighing the raw materials, adding them to ethanol, and stirring for 3 h to create a homogeneous solution. Then, the solution was transferred into the syringe to reach the fibrous form by the Electrospinning device. Finally, after drying and calcination, hollow nanofibers were formed. In this project, zinc acetate (Zn(CFl3C00)2.2Fl20; Merck) and copper acetate (Cu(CFl3COO) 2.H2o; Merck) were used as the main suppliers of zinc oxide and copper oxide, respectively. Also, ethanol (Merck) and polyvinylpyrrolidone (C6FI9NO) n, Mw = 40,000) were used as the solvent and fiber-forming polymer, respectively.

[0026] First, raw materials were weighed according to the concentration and molarity of the solution. Considering the desired molarities, zinc acetate and copper acetate salts were weighed and dissolved in ethanol solvent to obtain a completely clear solution. PVP was measured at different weight percentages and gradually added to the solution to give a completely clear solution. The dissolution process was performed for 3 h on the magnetic stirrer to ensure the complete dissolution of the materials. The fiber spinning process began using the electrospinning device by setting the injection rate of the solution and keeping the distance between the nozzle tip to the collector as well as the voltage constant. (Figure 1). Table 1 shows the parameters of the electrospinning device used in this project.

[0027] After preparing the primary fibers and collecting them from the collector surface, they were dried at 80 °C for 2 h and then calcined for 5 h at a constant temperature of 550 °C. Figure 2 shows a picture of samples before and after calcination.

[0028] The chemical composition of synthesized zinc oxide-copper oxide nanofibers is as follows (Table 2).

[0029] To study the characteristics and structure of synthesized nanofibers, XRD, OM, FESEM, DTA-TG, FTIR analyses, antibacterial tests using AATC100 standard method, and antiviral tests using IS018184 standard method were performed, the results of which are presented below. [0030] Evaluation of crystal structure and formed phases using X-ray diffraction (XRD) analysis

[0031] The most essential application of XRD is to determine the phases in an unknown sample. The location and intensity of peaks contain information from the sample, which can be used to determine the atomic structure and phase of the dispersing surfaces, and thus determine the type and structure of the unknown sample. This is performed by comparing the resulting diagram with the existing standards. In all materials, the crystalline structural properties, or the crystalline order, are not completely observed in the material, rather, the materials are a combination of amorphous and crystalline forms. Amorphous spheres form wide peaks and crystalline spheres form sharp peaks in the diagram. The intensity ratio of these peaks can be used to determine crystallinity. The mean size of the crystals is calculated by the Debye-Scherer relationship at full width half maximum (FWHM) according to the following equation:

[0032] where D represents the average size of the crystals perpendicular to the X-ray, K is the Debye-Scherer constant (0.9), l is the X-ray wavelength (0.154178 nm), and b is the peak width of half-maximum. The internal strain of the sample is calculated by the Williamson-Hall relationship as follows:

[0033] pcos0=(kA-D) +s.4sin0

[0034] where b is the full width of the Bragg peak at half maximum, k is the Scherer constant, D is mean crystallite size, l is the radiated X-ray wavelength, e is strain, and Q is peak angle.

[0035] According to the shape of the peaks obtained at angles 2Q = 31.77, 34.40, 36.26, 47.56, 56.62, 62.76, 66.44 belong to the hexagonal ZnO with Wurtzite structure (JCPDS 01-089-0510) and the peaks obtained at angles 2Q = 35.50, 38.77, 48.79, 58.33, and 61.62 are related to CuO with monoclinic structure (JCPDS 00-048-1548), and no peak related to impurities is observed. The crystal size is calculated using the peak width of half-maximum in the Debye-Scherer relationship and is as follows (Table 2).

[0036] The average size of crystallites calculated by the Debye-Scherer method (Table 3)

[0037] The average crystallite size (nm) of the sample

[0038] Z100 19.97 [0039] ZC5 18.75 [0040] ZC25 18.05

[0041] ZC50 17.19

[0042] ZC75 15.99

[0043] Analysis of the Size and Morphology of nanofibers Using Field Emission Scanning Electron Microscopy (FE-SEM) and Optical Microscopy (OM)

[0044] In the present project, the produced fibers were collected from the collector and evaluated at X1000 magnification using the TEM (Figure 2). It can be seen that the samples are in the form of fibers with a large length to diameter ratio and are reached as a shell-core. Therefore, according to the obtained images, the core-shell morphology (hollow nanofibers) can be observed in addition to solid nanofibers. Due to the limited magnification of the optical microscope and the more detailed study of the dimensions and morphology of the fibers obtained before and after calcination, a scanning electron microscope (SEM) was used.

Advantage effects of invention

[0045] Antibacterial properties of synthesized nanofibers [0046] Antiviral properties of synthesized nanofibers [0047] Antifungal properties of synthesized nanofibers [0048] ZnO - CuO composite hollow nanofibers

Brief description of drawings

[0049] [Fig. 1]: Overview of the device

[0050] [Fig. 2]: Overview of the device

[0051 ] [Fig. 3]: Device components without side cover [0052] [Fig. 4]: Electrical device parameters [0053] [Fig. 5]: Sample Z100, (a) before and (b) after calcination [0054] [Fig. 6]: Specifications of ZnO - (x% wt) CuO samples and their corresponding CuO weight percentages [0055] [Fig. 7]: X-ray diffraction spectrum of Z100, ZC5, ZC25, ZC50, ZC75 samples prepared by electrification method [0056] [Fig. 8]: The average size of crystals is calculated by Debye-Scherer method

[0057] [Fig. 9]: Transient optical microscope images [0058] [Fig. 10]: SEM images and EDX test results obtained from solid and hollow synthesized fiber samples (a) Z100 before calcination, (b) Z100, (c) ZC5, (d) ZC25, (e) ZC50 after calcination [0059] [Fig. 11]: The TG and DTA thermal analysis diagram shows the ZC25 sample

[0060] [Fig. 12]: Infrared spectroscopy (FT-IR) shows samples before and after calcination

[0061] FTIR chart: (A) Z100 sample before calcination, (B) Z100 sample after calcination and (C) ZC2 sample after calcination

Description of embodiments

[0062] [Fig. 1]: 1. Potential difference supply device 2. Syringe pump 3.

Syringe containing polymer solution 4. Metal nozzle 5. Screwdriver connector to the base 6. Electro-Motor 7. Polyurethane plate retaining holder 8. Gearbox 9. Collecting metal cylinder 10. Collected nanofibers 11. Polymer solution jets 12. Connection wires [0063] [Fig. 2]: Overview of the device [0064] [Fig. 3]: Device components without side cover [0065] [Fig. 4]: Electrical device parameters [0066] [Fig. 5]: Sample Z100, (a) before and (b) after calcination

[0067] [Fig. 6]: Specifications of Z n O - (x% wt ) CuO samples and their corresponding CuO weight percentages [0068] [Fig. 7]: X-ray diffraction spectrum of Z100, ZC5, ZC25, ZC50, ZC75 samples prepared by electrification method [0069] [Fig. 8]: The average size of crystals is calculated by Debye-Scherer method

[0070] [Fig. 9]: Transient optical microscope images [0071] [Fig. 10]: SEM images and EDX test results obtained from solid and hollow synthesized fiber samples (a) Z100 before calcination, (b) Z100, (c) ZC5, (d) ZC25, (e) ZC50 after calcination [0072] [Fig. 11]: The TG and DTA thermal analysis diagram shows the ZC25 sample

[0073] [Fig. 12]: Infrared spectroscopy (FT-IR) shows samples before and after calcination

[0074] FTIR chart: (A) Z100 sample before calcination, (B) Z100 sample after calcination and (C) ZC2 sample after calcination

Examples

[0075] The proposed design can be produced and used as a coating to add anti-viral, anti-bacterial, and anti-fungal properties to various woven and nonwoven fabrics in different medical and general masks, gowns, air filters, etc. Padding, exhaustion, spray, cavitation, ultrasonic bath, and coating layer using foam are among the methods of coating this product on fabrics.

Industrial applicability

[0076] The industrial application of this design is related to the field of fabrics, protective clothing, and fabric filters. Since this design can be applied on all kinds of clothes, breathing masks, hospital clothes, sheets, furniture, carpets, air conditioning system filters for industrial, hospital, home, & car use, as well as industrial and home water purification system filters, because, in addition to increasing the filtration power, they will also have antimicrobial (antiviral, antibacterial, and antifungal) properties.

Claims

[Claim 1] The proposed design is the process of synthesis and production of zinc oxide-copper oxide composite nanofibers with AZnO-BCuxO formulation (A = 0.95, B = 0.05, X = 1 ,2) with the ability to coat all types of fabrics with antimicrobial properties. In this project, the precursors of zinc acetate, copper acetate were used as the main suppliers of zinc oxide and copper oxide, respectively; ethanol was used as the solvent, and polyvinylpyrrolidone was the fiber-forming polymer for synthesis.

[Claim 2] According to Claim 1 , the production of hollow composite nanofiber ZC5 with the Chemical formulation AZnO-BCuxO (A = 0.95, B = 0.05, X = 1 ,2) has anti-coronavirus (n-SARS-CoV2 virus) properties with an efficiency of >99%.

[Claim 3] According to Claim 2, the production of anti-coronavirus fabric by airless jet spray method and hot press (simultaneously) with the efficacy of >99% against coronavirus.