WO2021188073A1

WO2021188073A1 - Webs with coaxial nanofiber structure, a textile product containing these webs and a preparation method thereof

Info

Publication number: WO2021188073A1
Application number: PCT/TR2020/050936
Authority: WO
Inventors: Nihal SARIER; Emel ONDER KARAOGLU
Original assignee: Istanbul Kultur Universitesi
Priority date: 2020-03-16
Filing date: 2020-10-12
Publication date: 2021-09-23
Also published as: TR202004019A2

Abstract

The present invention relates to webs with coaxial nanofiber structure that can perform heat management in low temperature (T<18°C), normal temperature (18°C<T<43°C) and high temperature (43°C<T<70°C) regions; a textile product (10) containing these webs; and a preparation method of this product. The webs (1) with coaxial nanofiber structure contain fatty acid esters in the extract part and polymers in the shell part. Whereas the textile product (10) consists of array of the textile surface (12)-the fusible interlining (ll)-the web (1) with nanofiber structure-the fusible interlining (ll)-the textile surface (12).

Description

WEBS WITH COAXIAL NANOFIBER STRUCTURE, A TEXTILE PRODUCT CONTAINING THESE WEBS AND A PREPARATION

METHOD THEREOF

Technical Field

The present invention relates to webs with coaxial nanofiber structure that can perform heat management in low temperature (T<18°C), normal temperature (18°C<T<43°C) and high temperature (43°C<T<70°C) regions; a textile product containing these webs; and a preparation method of this product.

Background of the Invention

Today, research groups from various disciplines and industry are interested in thermal regulation function of new materials and composites in a very broad sense. Global demand for new technologies which can provide energy saving; more comfortable, healthier and environmentally friendly products; and sustainable designs have been the main driving force for developing various products with superior thermal characteristics.

Dynamic heat management is a new concept used for heat exchange of various systems with the environment. Functional materials being able to store heat and regulate temperature can be used for the purpose of heat management. “Smart” textiles being capable of performing dynamic heat management and sensitive to temperature changes of the environment are functional textile products which are used in clothing systems; in textile products such as tents, blankets, etc. for protection against cold and hot environments; in buildings; in automotive, aerospace industry; biomedical applications; in applications such as temperature sensitive packaging, solar panels, etc. Although there are some successful applications in these areas, new approaches are needed in order to produce new and innovative products with active thermal management capability.

Thermal energy storage (TES) is a method that has a great potential for different thermal applications. Creation of composite systems that can absorb heat from the environment when the ambient temperature rises, store the energy it absorbs and dissipate heat to the environment when the ambient temperature decreases by utilizing high heat absorption and release capacities of materials called as “phase change material (PCM)” in the phase change processes is one of the active or dynamic heat management methods by TES. Phase change materials are inorganic or organic substances capable of performing a repeated conversion between solid- liquid or solid-solid phases. Today, there are more than five hundred phase change materials known as synthetic or natural. These materials vary by their phase change temperatures or thermal capacities.

Addition of phase change materials to the final product is a challenging research and application subject that is full of opportunities. Solid-liquid PCMs are introduced into an organic or inorganic carrier material added to the structure directly, in order to perform dynamic heat management in various systems. Thereby, their thermal properties can be utilized. Various methods are tried and applied so as to perform dynamic heat management with solid-liquid organic PCMs in textiles. PCMs are expected to improve heat management of textile materials; repeatability of the heat absorption and release process; to prevent PCMs from evaporating, melt flowing and mixing into textile structure; to improve their thermal stability, thermal conductivity properties; and not to affect mechanical properties and other quality properties of the final product adversely as well. Therefore, it is required to develop of form-fixed PCMs to enhance applicability and energy conversion efficiency. In this context, new products are needed to apply these materials to textiles and similar systems easily and to use these effectively for the purpose of using phase changing materials more effectively. The Korean patent document no. KR20090084208, an application in the state of the art, discloses a polymer fiber which is obtained as a result of coating the phase change material with an organic polymer. Electro spinning method is used for this and a phase change material is used as core and organic polymer is used as coating layer. A nonwoven fabric with a latent heat storage characteristic can be obtained from the said polymeric fiber. This fabric creates a thermal transfer and a heat storage medium. The polymer used in the coating layer can be nylon-6, polystyrene, polyvinylpyrrolidone, polyurethane, polyester, polymethyl methacrylate, polyvinyl alcohol and poly acrylonitrile. Whereas the phase change material can be n-octacoic acid, n-heptacoic acid, n-hexacoic acid, n-tetracoic acid, n-tricoic acid, n-docoic acid, n-heneic acid, n-acoic acid, n Nonadecane, n- octadecane, n-heptadecan n-hexadecane, n-pentadecane, n-tetradecane or n- tridecane alone or used in combination of two or more thereof.

The Chinese patent document no. CN103061039, another application in the state of the art, discloses a method of manufacturing a polymer composite material. In one embodiment, a set of microcapsules containing a phase change material are mixed with a polymeric material. Latent heat of the dispersing polymeric material is at least 40 J/g and its transition temperature is in the range of 0°C to 50°C. The first blend is processed to form a polymer compound. A variety of polymeric composite shapes can be formed such as pellets, fibers, flakes, sheets, films, rods, and so forth. The polymeric composite can be used as is or incorporated in various articles where a thermal regulating properties are desired. Textile products and clothes can be given as examples of these articles. The polymeric composite have the ability to absorb and release thermal energy under different environmental conditions. The phase change materials include a variety of organic and inorganic substances. Examples of phase change materials include hydrocarbons (e.g., straight or paraffinic, branched alkanes, unsaturated hydrocarbons, halogenated hydrocarbons, and alicyclic hydrocarbons), hydrated salts (e.g., calcium chloride hexahydrate, hexahydrate, calcium bromide, magnesium nitrate hexahydrate, lithium nitrate trihydrate, potassium fluoride tetrahydrate, ammonium alum, magnesium chloride hexahydrate, sodium carbonate decahydrate, disodium phosphate dodecahydrate, sodium sulfate decahydrate, and sodium acetate trihydrate), waxes, oils, water, fatty acids, fatty acid esters, dibasic acids, dibasic esters, 1 -halides, primary alcohols, aromatic compounds. Examples of dispersed polymeric materials include polyamides (e.g., Nylon 6, Nylon 6/6, Nylon 12, polyaspartic acid, polyglutamic acid, and so forth), polyamines, polyimides, polyacrylics (e.g., polyacrylamide, polyacrylonitrile, esters of methacrylic acid and acrylic acid, and so forth), polycarbonates (e.g., polybisphenol A carbonate, polypropylene carbonate, and so forth), polydienes (e.g., polymer Butadiene, polyisoprene, polynorbornene, and so forth), polyepoxides, polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylenephthalate phthalate Propylate) dicarboxylate, polycaprolactone, polyglycolide, polylactide, polyhydroxybutyrate, polyhydroxyvalerate, polyethylene adipate, polybutylene adipate, polyamide propylene glycol, and so forth, poly ethers (e.g., polyethylene glycol (polyethylene oxide), polybutylene glycol, polypropy)polyoxymethylene (p-formaldehyde), polytetramethylene ether (polytetrahydrofuran), polyepichlorohydrin, and so forth), polyflourocarbons, formaldehyde polymers (e.g., urea-formaldehyde, melamine-formaldehyde, phenol formaldehyde, and so forth), natural polymers, chuantos, chitos lignin, waxes, and so forth), polyolefins (e.g., polyethylene, polypropylene, polybuten, polyolefin, and so forth), polyphenylenes (e.g., polyphenylene ether, polyphenylene sulfide, polyphenylene ether sulfone, and so forth), silicon containing polymers (e.g., polydimethyl siloxane, polycarbomethyl silane, and so forth), polyurethane, polyvinyl resin (e.g., polyvinyl butyral, polyvinyl alcohol, polyvinyl acetate, polystyrene, polymethyl styrene, polyvinyl chloride, polyvinyl pryrrolidone, polymethyl vinyl ether, poly ethyl vinyl ether, polyvinyl methyl ketone, and so forth), poly acetals, polyarylates and copolymers (e.g., polyethylene-co-vinyl acetate, polyethylene- co-acrylic acid, polybutylene terphthalate-co-polytetramethylene terephthalate, polylauryllactam-block-polytetrahydrofuran, and so forth) and mixtures thereof. Summary of the Invention

An objective of the present invention is to realize webs with coaxial nanofiber structure which can perform heat management in low temperature (T<18°C), normal temperature (18°C<T<43°C) and high temperature (43°C<T<70°C) regions; wherein fatty acid esters are used as extract and various polymers are used as shells; and a nanocomposite textile product containing these webs.

Another objective of the present invention is to realize a webs with coaxial nanofiber structure wherein fatty acid esters of different chain lengths are used as extract and polyacrylo nitrile (PAN) or polymethacrylic acid-co-ethyl acrylate (PMEA) is used as shell; which have characteristic of performing smooth, cylindrical, thermal cycle and which are also chemically stable, thin, flexible and have mechanical strength; and a textile-based textile product containing these webs.

Detailed Description of the Invention

“Webs with Coaxial Nanofiber Structure and a Textile Product Containing these Webs” realized to fulfil the objectives of the present invention is shown in the figures attached, in which:

Figure 1. a) SEM image (xl5000) of the sample with 6PAN20methylpalmitate code and b) fiber diameter distribution histogram of the SEM image.

Figure 2. a) SEM image of the sample with 15PMEA20methylpalmitate code and b) fiber diameter distribution histogram of the SEM image.

Figure 3. DSC curves of a) 6PAN-20methylpalmitate and b) 6PAN- 20isopropylpalmitate at the 100^th heating-cooling cycle.

Figure 4. Comparative FTIR spectra of 6PAN20 methyl palmitate and PAN. Figure 5. a) DSC 2^nd and 4^th cycle heating-cooling curves (10°C min ¹), b) SEM image (15000x) and c) fiber diameter distribution of SEM image of 15PMEA20methylpalmitate bicomponent nanoweb sample.

Figure 6. Comparative FTIR spectra of 15PMEA20methylpalmitate, methyl palmitate and PMEA.

Figure 7. A drawing of a multilayer product containing PAN-FAE or PMEA-FAE nanoweb.

Figure 8. DSC curves of the sample with C5 (content: 6PAN20methylpalmitate) code at the 2^nd and 10^th heating-cooling cycles.

Figure 9. DSC curves of the felt sample with E3 (content: 6PAN20methylpalmitate) at the 2^nd and 10^th heating-cooling cycles.

The components illustrated in the figures are individually numbered, where the numbers refer to the following:

I . Web with nanofiber structure

10. Textile product

I I . Fusible interlining

12. Textile surface

The inventive webs (1) with coaxial nanofiber structure being capable of heat management comprises: fatty acid esters in the extract part; polymers in the shell part

The fatty acid esters (FAEs) contained by the inventive webs (1) with coaxial nanofiber structure are bio-based fatty acid alkyl esters or fatty acid vinyl esters which have different molecular weight and chain length, do not lose their high heat capacity, are thermally stable and non-toxic. The said fatty acid alkyl esters have a general formula of C_nFh_n+iOOR; R (alkyl) included in the general formula is represented as -C_nFh_n+i and n can take any of 10, 12, 14, 16 and 18 values. The said fatty acid vinyl esters have a general formula of C_nFh_n+iOOR; R (vinyl) included in the general formula is represented as -CH=CH2 and n can take any of 10, 12, 14, 16 and 18 values. Fatty acid esters are used as solid-liquid phase change material (PCM). In one embodiment of the invention, fatty acid esters can be any of methyl palmitate, ethyl palmitate, palmityl palmitate, isopropyl palmitate, isopropyl myristate, butyl stearate or vinyl stearate. In order that the said fatty acid esters can be used within webs with nanofiber structure, their solutions are prepared by dissolving these in DMAc (dimethylacetamide) or ethanol. For the specimens of these fatty acid esters, the phase conversion characteristics measured at the 2^nd and 10^th heating-cooling cycle by differential Scanning Calorimetry (DSC) were examined and the results are given in the Table 1

Table 1. Phase conversion characteristics of some fatty acid esters measured by DSC at the 2^nd and 10^th heating-cooling cycle (5°Cmin ¹)

The DSC results included in the Table 1 indicate that fatty acid esters have characteristics suitable for dynamic heat management studies in low (T<18°C), normal (18°C<T<43°C) and high temperature (43°C<T<70°C) regions and they can maintain their thermal characteristics at the heating-cooling cycles.

The polymer contained by the inventive webs (1) with coaxial nanofiber structure is polyacrylo nitrile (PAN) and/or polymethacrylic acid-co-ethyl acrylate (PMEA). In order that polymers can be used in the shell part of the web (1) with nanofiber structure, PAN is dissolved within DMAc (dimethylacetamide) whereas PMEA is dissolved within ethanol and thereby their solutions are prepared. Shell- solution concentrations are in the form of 4-10% PAN and 8-20% PMEA within DMAc. In one embodiment of the invention, production parameters selected for combining fatty acid ester and polymers with the web structure having nanofiber structure are summarized in the Table 2.

Table 2. Production parameters selected for production of nanoweb wherein fatty acid esters are used as extract

Parameter Parameter definition Values xi Type of shell PAN, PMEA

X2 Type of shell solvent DMAc for PAN, Ethanol for PMEA

Concentration of shell X3 solution 6% PAN; 15% PMEA

X4 Type of extract FDM Different fatty acid esters

X5 Type of extract solvent DMAc or Ethanol

Concentration of extract X6 solution %20

X7 Applied voltage 10-32 kV

X8 Collector distance 15 cm

X9 Injector spraying rates 0.01-0.06 mLsa ¹

X10 Electrospinning time 30 min

X 11 Ambient temperature 24-25 °C In a preferred embodiment of the invention, the parameters in the electrospinning experiments comprising the fatty acid esters and the shells that are used for obtaining the webs (1) with nanofiber structure are given in Table 3 and Table 4. The parameters in the electrospinning experiments wherein fatty acid esters prepared within 6% PAN as shell and DMAc at a concentration of 20% as extract are included in the Table 3 and the parameters in the electrospinning experiments wherein fatty acid alkyl esters prepared within 15% PMEA as shell and ethanol at a concentration of 20% as extract are included in the Table 4. Table 3. Parameters used in electrospinning experiments carried out by 20% fatty acid ester (four different YAAEs selected as an example) within 6% PAN as shell and DMAc as extract

Shell Extract Injector Collector

Distance pump pump Voltage Voltage Time

Specimen (cm) (mL/sa) (mL/sa) (kV) (kV) (min)

6PAN20isopropylmyristate _{15 0}.08 0.06 +10.0 -9.0 30

6PAN20isopropylpalmitate 15 0.08 0.06 +10.0 -9.0 30

6PAN20butylstearate ₁₅ o.08 o.06 _{+9 0} -8.0 30

6PAN20methylpalmitate ₁₅ 0_,05 0.04 +6.5 -6.5 30

Table 4. Parameters used in electrospinning experiments carried out by 20% fatty acid ester within 15% PMEA as shell and ethanol as extract

Shell Extract ^Ini^ector Collector pump pump Voltage Voltage Time

Specimen (mL/sa) (mL/sa) (kV) (kV) (min)

15PMEA20isopropylmyristate 0.04 0.03 +12.5 -10.5 30

15PMEA20isopropylpalmitate 0.04 0.03 +12.2 -12.0 30

15PMEA20butylstearate 0.04 0.03 +12.0 -11.0 30

15PMEA20methylpalmitate 0.04 0.03 +12.5 -10.0 30

The inventive webs (1) with nanofiber structure are combined through the use of fatty acid esters (FAEs) as extract and PAN or PMEA as shell by coaxial electrospinning. The webs (1) with nanofiber structure can perform heat management in low temperature (T<18°C), normal temperature (18°C<T<43°C) and high temperature (43°C<T<70°C) regions. Characterization tests were carried out for the PAN-FAE and PMEA-FAE bicomponent nanowebs prepared and the results obtained are given below.

SEM images of the webs (1) with nanofiber structure comprising the inventive PAN-FAE components were examined. SEM image of the sample with 6PAN20methylpalmitate code and fiber diameter distribution histogram of the SEM image are included in Figure la and Figure lb respectively. Here, the fibers are cylindrical, smooth-surfaced and they don’t comprise knot and they are approximately 90 - 100 pm long. Fiber diameter distribution varies in the range of 1511 nm and 44 nm and it indicates a fiber formation that is inclined to left, very fine and fine fiber formation. Average fiber diameter is calculated as 359±93 nm. SEM image of the sample with 15PMEA20methylpalmitate code and fiber diameter distribution histogram of the SEM image are included in Figure 2a and Figure 2b respectively. The fibers are cylindrical, smooth-surfaced and they don’t comprise knot and they are approximately 90 - 100 pm long. Fiber diameter distribution varies in the range of 1367 nm and 33 nm and it indicates a fiber formation that is inclined to left, very fine and fine fiber formation. Average fiber diameter is calculated as 259±81 nm. The SEM images do not show any material (FAE) extending beyond the nanofibers.

Thermal characteristics of the webs (1) with nanofiber structure containing the inventive PAN-FAE compounds were examined. The thermal properties of nanofiber networks (1) containing PAN-FAE compounds of the invention were examined. Heat absorption and dissipation capacity of the PAN-FAE electrospun nanowebs vary in the range of 30-102 Jg ¹. Thermal behaviours of four different PAN-FAE nanowebs at the 10^th heating-cooling cycle are given as an example in Table 5 for DSC behaviours of the samples; whereas thermal behaviours of two different samples at the 100^th heating-cooling cycle are given as an example in Table 3 for thermal cycle characteristics. Table 5. Phase conversion characteristics of four different sample bicomponent nanowebs at the 10^th heating and cooling cycles of by DCS, wherein 6% PAN is used as shell and 20% fatty acid ester solutions are used as extract (10°C min ¹)

10^th Cycle heating 10^th Cycle cooling

LH l_{cu l} end (Jg ' ) Tbeg- Tend DH (Jg ' )

Specimen (°C) (> 0) (°C) (< 0)

6PAN20isopropylmyristate -9-9 46 -8- -17 47

6PAN20isopropylpalmitate 7-18 78 10- -4 77

6PAN20butylstearate 16-23 47 19-9 49

6PAN20methylpalmitate 28-32 102 25-4 100

When thermal characteristics of the webs (1) with nanofiber structure comprising the inventive PAN-FAE compounds were examined, the temperature range of the solid-liquid phase change at the 100^th heating cycle measured by DSC of the samples with 6PAN20methylpalmitate and 6PAN20isopropylpalmitate code - which are quite successful in terms of nanofiber formation- were measured as 28- 33 °C and 9-14 °C respectively; the corresponding heat capacities were determined as 102 Jg ¹ and 81 Jg ¹. Leftward shifts observed at the cooling cycle are consistent with the tendency of fatty acid esters to overcool. The fact that no change occurs in the ranges of phase change temperature and the heat capacity at the 100^th heating-cooling cycles indicates that the samples are thermally stable and suitable for repetitive use. Consequently, the PAN-FAE nanowebs wherein fatty acid esters are used as extract and the PAN is used as shell are successfully obtained as webs (1) with nanofiber structure that has thermal cycle characteristic and is thermally stable as well.

FTIR behaviours of the webs (1) with nanofiber structure comprising the inventive PAN-FAE compounds were examined. FTIR results of the 6PAN-FAE shell-extract nanowebs are such as to support SEM and DSC analysis. As an example to FTIR spectra of 6PAN-FAE nanowebs, for example FTIR spectrum with 6PAN20methylpalmitate code is included in the Figure 4 in comparison with methylpalmitate and PAN. Characteristic vibrations of PAN and methylpalmitate groups are clearly observed in FTIR spectrum of the nanoweb samples. FTIR spectra of nanowebs indicate that fatty acid esters are kept within PAN shell successfully.

Thermal characteristics of the webs (1) with nanofiber structure containing the inventive PMAE-FAE compounds were examined. According to the phase conversion characteristics of the 15PMEA-FAE bicomponent nanowebs measured by DSC at the 10^th heating-cooling cycles and summarized in the Table 6, the heat capacities of the samples were measured in the range of 33-110 Jg ¹ and the phase conversion were consistent with the phase conversion temperature range (in the Table 1) of the fatty acid esters used as extract. As an example to DSC behaviours of the samples, DSC heating-cooling measurements of the 15PMEA20methylpalmitate bicomponent nanoweb sample are shown in the Figure 5a. When the DSC chart of the sample with 15PMEA20methylpalmitate code wherein methylpalmitate (ethanol) solution in the ratio of 20% was used as extract and 15% PMEA (ethanol) solution was used as shell, measured by DSC at the 2^nd and 4^th heating-cooling cycles and given in the Figure 5a is examined; it is seen that the phase change in the heating cycle occurs in the range of 28°C-33°C and the total heat absorbed is measured as 110 Jg ¹. It is seen that the phase change in the cooling cycle occurs in the range of 25°C-22°C and the heat released is measured as DH = 105 Jg ¹. The heat capacity of the bicomponent nanoweb sample with 15PMEA20methylpalmitate code corresponds to 47% of 237 Jg ¹ value which is the heat capacity of methyl palmitate.

Table 6. Phase conversion characteristics of four different PMEA-FAE bicomponent nanowebs at the 10^th heating and cooling cycles of by DCS, wherein 15% PMEA is used as shell and 20% FAE solutions are used as extract (10°Cmin 10^th Cycle heating 10^th Cycle cooling

AH AH

Tbeg- Tend (Jg ' ) Tbeg- Tend (Jg ' )

Specimen (°C) (> 0) (°C) (< 0)

15PMEA20isopropylmyristate -5-8 40 -6- -23 42

15PMEA20isopropylpalmitate 10-16 63 10- 5 65

15PMEA20bulylstearate 5-23 33 20-2 34

15PMEA20methylpalmitate 28-37 110 25-22 105

SEM images of the webs (1) with nanofiber structure comprising the inventive PMAE-FAE components were examined. When the SEM image of the sample with 15PMEA20methylpalmitate given in the Figure 5b and the fiber distribution given in the Figure 5c are examined, it is seen that cylindrical, smooth-surfaced thin fibers are obtained; distribution of the fiber diameters vary in the range of 1367 nm and 33 nm; the average diameter of the fibers is 259±81 nm.

FTIR behaviours of the webs (1) with nanofiber structure comprising the inventive PMAE-FAE components were examined. FTIR results of the 15PMEA- FAE shell-extract nanowebs are such as to support SEM and DSC analysis. As an example to FTIR spectra of 15PMEA- FAE nanowebs, for example FTIR spectrum with 15PMEA20methylpalmitate code is included in the Figure 6 in comparison with methylpalmitate and PMEA. Characteristic vibrations of PMEA and methylpalmitate groups are clearly observed in FTIR spectrum of the nanoweb samples. FTIR spectra of nanowebs indicate that fatty acid esters are kept within PMEA shell successfully.

With the invention, it is enabled to use PAN shell or PMEA shell and fatty acid esters within the nanoweb structure (1) upon form-fixing. Other polymers used in fiber production in the industry can also be used as shells: i) specimen with 6PAN20methylpalmitate code which can perform repetitive phase conversion in the temperature range of 28°C-32°C and has a heat absorption capacity of 75 Jg ^x, average fiber diameter of 359 nm and wherein 6% PAN(DMAc) solution is used as shell and 20% methylpalmitate (DM Ac) solution is used as extract; and ii) specimen with 15PMEA20methylpalmitate code which can perform repetitive phase conversion in the temperature range of 28°C-32°C and has a heat absorption capacity of 110 Jg ¹, average fiber diameter of 259 nm and wherein 15% PMEA(ethanol) solution is used as shell and 20% methylpalmitate (ethanol) solution is used as extract stand out by their nanofiber characteristics and heat capacities.

The invention also relates to a nanocomposite textile product (10) containing web (1) with PAN-FAE and PMEA-FAE nanofiber structure.

The inventive textile product (10) with nanocomposite structure comprises: at least one web (1) with nanofiber structure which is used as phase change material; at least one fusible interlining (11) between which the webs (1) with nanofiber structure are disposed; and at least one textile surface (12) between which the fusible interlinings (11) comprising the webs (1) with nanofiber structure are disposed.

The webs (1) with nanofiber structure included in the inventive textile product (10) are composed by combining fatty acid esters (FAEs) as extract and PAN or PMEA polymers as shell by means of electrospinning.

The fusible interlining (11) included in the inventive textile product (10) is a fixing material made of cotton or wool wherein all kinds of adhesive material are impregnated.

The textile surface (12) included in the inventive textile product (10) is any of a layer made of a cotton/wool/synthetic polymer/bio-based woven fabric in different gram/m² densities or felt layers or nonwoven surfaces prepared from all these starting materials specified. The method of preparing the inventive textile product (10) includes procedure steps of disposing the web (1) with nanofiber structure between two thin-layer fusible interlinings (11), then laying the composite prepared in the form of the fusible interlining (1 l)-the web (1) with nanofiber structure-the fusible interlining (11) respectively between two textile surfaces (12). Finally in the method, the composite structure prepared according to array of the textile surface (12)-the fusible interlining (l l)-the web (1) with nanofiber structure-the fusible interlining

(11)-the textile surface (12) as shown in the Figure 7 is kept between wax paper, in a rotary cylinder system that is pre-set in a temperature range of 100-200 °C under optimum pressure of 1-5 bar, for an optimum period of 10-60 seconds, then made ready upon being removed from the other end.

Tensile behaviours of the textile product with multilayer composite structure consisting of nanowebs (1) fixed between the inventive nonwoven textile surfaces

(12) by the fusible interlining (11) were examined and the examined specimen are shown in the Table 7. Analyses were carried out for this examination by using large tensile modulus in METTLER TOLEDO dynamic mechanical analyzer (DMA/SDTA861), at 25°C, at a frequency of lHz and applying forces varying in the range of 0.1 N-1.0 N. Jaw distance is 19 mm in DMA tensile tests. Forces were applied to the specimens in the range of 0.1-1.0 N continuously at a frequency of 1 Hz by means of movable jaws.

Table 7. Multilayer composite products containing PAN-FDM bicomponent nanoweb (C5= nonwoven surface, 25 gm ², E3= Felt 150 gm ²) (Thickness=0,5 cm)

Weight of

Nonwove Weight of Total

Total n Surface Nanoweb Weight/Are

Specimen Nanoweb contained mass (g) (g) (g) a (g/m²)

C(Controll) 0.00608 0.00608 0.00000 77 C5 6PAN20methylpalmitate 0.02648 0.00608 0.02040 337

E(Control) 0.01808 0.01808 0.00000 230

E3 6PAN20methylpalmitate 0.03877 0.01808 0.02069 494

Some studies were carried out for characterization detection of the textile products (10) with the inventive nanoweb. DSC curves with ten heating-cooling cycles of the textile composites with C5 (content: 6PAN20metilpalmitat) and E3 (content: 6PAN20metilpalmitat) code -names and some characteristics of which are given in the Table 7- are shown in the Figure 8 and the Figure 9. DSC curves of the nanowebs comprised by the DSC curves in the 2^nd and 10^th heating-cooling cycles of the specimen with C5 code shown in the Figure 8 are essentially consistent with the DSC curves of the nanowebs comprised by thereof. When the DSC chart of the 10^th heating-cooling cycle of the specimen with C5 code is examined, it is seen that the phase change in the heating cycle occurs in the range of 13°C-32°C and the total absorbed heat is measured as 34 Jg ¹. It is seen that the phase change in the cooling cycle occurs in the range of 23°C-2°C and the total released heat is measured as 33 Jg ¹.

In all samples (1) with nanoweb structure contained by the inventive textile products (10), no significant change occurred at heat capacities in ten heating cooling cycles and ranges of phase conversion temperature. These findings indicate the thermal stability of the composite structure produced and they also show that no leakage is included in the structure.

DSC curves of the felt samples with E3 (6PAN20methylpalmitate) code, one of the inventive textile products (10), are shown in the 2^nd and 10^th heating-cooling cycles in the Figure 9. The DSC curves of the E3 in the 2^nd and 10^th heating cooling cycles are essentially consistent with the DSC curves of the nanowebs comprised by thereof (in Figure 5, Table 1 and Table 6). When the DSC chart of the 10^th heating-cooling cycle of the specimen with E3 code is examined, it is seen that the phase change in the heating cycle occurs in the range of 16°C-23°C and the total absorbed heat is measured as 35 Jg ¹. It is seen that the phase change in the cooling cycle occurs in the range of 16°C-10°C and the total released heat is measured as 25 Jg ¹. In all samples, no significant change occurred at heat capacities in ten heating cooling cycles and ranges of phase conversion temperature. These findings indicate the thermal stability of the composite structure produced and they also show that no leakage is included in the structure.

With their heat capacities, heat absorption-release temperature ranges, thermal stabilities, sealing characteristics, and due to the fact that they exhibit high thermal insulation and high thermal effusion values, engineering stress values of 150 MPa and above; the inventive textile products (10) with composite structure consisting of PAN-FAE and PMEA-FAE nanofiber (1) that is fixed between two textile surfaces (12) by means of the fusible interlining (11) are very suitable for applications to be performed in low (T<18°C), normal (18°C<T<43°C) and high temperature (43°C<T<70°C) temperature ranges. Dispersion of the phase change material within the host material, evaporation and reaction of the phase change material with the external environment can be avoided with the nanofibers (1) which are composed by use of polymers as shell and fatty acid esters as extract in the textile products (10); the heat transfer area is increased extraordinarily by means of the very fine nanofiber structure; and nanoweb volume containing fatty acid ester can remain constant. Thereby, they can be easily applied in textile structures without inhibiting other characteristics of host textiles and normal use conditions are not affected.

The inventive textile product (10) can be used as inner packaging material in transport boxes of medical products such as medicine, blood and blood derivatives, serum that must be stored and transported below a certain temperature (2°C<T<18°C) and biomedical products; in storage and transport containers (T<0°C) of ready-made foods such as ice cream, cooked fish and meat and cold drinks; in biotechnology; in production of cold therapy materials; in biomedical materials intended for thermal therapy; in wearable thermal sensors; in cold and hot climate sportswear; in clothing systems for very hot climates; for utilizing solar energy; in thermoelectric system designs and in electronic circuit protections. In addition, the PAN-FAE or PMEA-FAE structures contained in the inventive textile product (10) can be used separately or in combination in buildings; accommodation places such as tents and so on; vehicles such as cars and planes for temperature-controlled transportation.

Within these basic concepts; it is possible to develop various embodiments of the inventive webs (1) with coaxial nanofiber structure and a textile product containing these webs; the invention cannot be limited to examples disclosed herein and it is essentially according to claims.

Claims

1. Webs (1) with coaxial nanofiber structure being capable of heat management; characterized in that they comprise: - fatty acid esters in the extract part; polymers in the shell part.

2. A web (1) with coaxial nanofiber structure according to Claim 1; characterized by fatty acid esters (FAEs) which are bio-based fatty acid alkyl esters or fatty acid vinyl esters that have different molecular weight and chain length, do not lose their high heat capacity, are thermally stable and non-toxic.

3. A web (1) with coaxial nanofiber structure according to any of Claim 1 or 2; characterized in that it is a fatty acid alkyl ester having a general formula of C_nH_2n+iOOR; R (alkyl) included in the general formula is represented as -C_nH_2n+i and n can take any of 10, 12, 14, 16 and 18 values.

4. A web (1) with coaxial nanofiber structure according to any of Claim 1 or 2; characterized in that it is a fatty acid vinyl ester having a general formula of C_nFh_n+iOOR; R (vinyl) included in the general formula is represented as -CH=CH2 and n can take any of 10, 12, 14, 16 and 18 values.

5. A web (1) with coaxial nanofiber structure according to any of the preceding claims; characterized by fatty acid esters which are used as solid-liquid phase change material (PCM).

6. A web (1) with coaxial nanofiber structure according to any of the preceding claims; characterized by a fatty acid ester which is any of methyl palmitate, ethyl palmitate, palmityl palmitate, isopropyl palmitate, isopropyl myristate, butyl stearate or vinyl stearate.

7. A web (1) with coaxial nanofiber structure according to any of the preceding claims; characterized by fatty acid esters which can be used upon their solutions are prepared dissolving these in DMAc (dimethylacetamide) or ethanol.

8. A web (1) with coaxial nanofiber structure according to any of the preceding claims; characterized by the polymer which is polyacrylo nitrile (PAN) and/or polymethacrylic acid-co-ethyl acrylate (PMEA).

9. A web (1) with coaxial nanofiber structure according to any of the preceding claims; characterized by the polymer which is usable upon PAN is dissolved within DMAc (dimethylacetamide) whereas PMEA is dissolved within ethanol.

10. A web (1) with coaxial nanofiber structure according to any of the preceding claims; characterized in that shell-solution concentrations are in the form of 4-10% PAN and 8-20% PMEA within DMAc.

11. A nanocomposite textile product (1) comprising the web (1) with PAN- FAE and PMEA-FAE nanofiber structure according to any of the preceding claims.

12. A textile product (10) according to Claim 11; having a nanocomposite structure, characterized by at least one web (1) with nanofiber structure which is used as phase change material; - at least one fusible interlining (11) between which the webs (1) with nanofiber structure are disposed; and at least one textile surface (12) between which the fusible interlinings (11) comprising the webs (1) with nanofiber structure are disposed.

13. A textile product (10) according to any of Claim 12 or 13; characterized by webs (1) with nanofiber structure which are composed by combining fatty acid esters (FAEs) as extract and PAN or PMEA polymers as shell by means of electrospinning.

14. A textile product (10) according to any of Claim 11 to 13; characterized by the fusible interlining (11) which is a fixing material made of cotton or wool wherein all kinds of adhesive material are impregnated.

15. A textile product (10) according to any of Claim 11 to 14; characterized by the textile surface (12) which is any of a layer made of a cotton/wool/synthetic polymer/bio-based woven fabric in different gram/m² densities or felt layers or nonwoven surfaces prepared from all these starting materials specified.

16. A method characterized by the steps of disposing the web (1) with nanofiber structure between two thin-layer fusible interlinings (11), then laying the composite prepared in the form of the fusible interlining (1 l)-the web (1) with nanofiber structure-the fusible interlining (11) respectively between two textile surfaces (12), finally during preparation of a textile product according to any of Claim 11 to 15, keeping the composite structure prepared according to array of the textile surface (12)-the fusible interlining (ll)-the web (1) with nanofiber structure-the fusible interlining (1 l)-the textile surface (12) between wax paper, in a rotary cylinder system that is pre-set in a temperature range of 100-200 °C under optimum pressure of 1-5 bar, for an optimum period of 10-60 seconds, then making it ready upon being removed from the other end.

17. A textile product (10) according to any of Claim 11 to 15; which is used as inner packaging material in transport boxes of medical products such as medicine, blood and blood derivatives, serum that must be stored and transported in a temperature range of 2°C-18°C and biomedical products; in storage and transport containers (T<0°C) of ready-made foods such as ice cream, cooked fish and meat and cold drinks; in biotechnology; in production of cold therapy materials; in biomedical materials intended for thermal therapy; in wearable thermal sensors; in cold and hot climate sportswear; in clothing systems for very hot climates; for utilizing solar energy; in thermoelectric system designs and in electronic circuit protections

18. A textile product (10) according to any of Claim 11 to 15; wherein PAN- FAE or PMEA-FAE structures can be used separately or in combination in buildings; accommodation places such as tents and so on; vehicles such as cars and planes for temperature-controlled transportation.