Method for preparing highly cut-resistant ultrahigh molecular weight polyethylene (UHMWPE) fiber and use thereof

Abstract

The present invention discloses a highly cut-resistant ultrahigh molecular weight polyethylene fiber, made of a ultrahigh molecular weight polyethylene and an inorganic ultrafine micropowder having a nanocrystalline structural morphology, wherein the inorganic ultrafine micropowder is one of an oxide, carbide, and nitride of aluminium, titanium, silicon, boron, and zirconium, or a combination thereof, and has an average diameter of 0.1-300 m and a content of 0.1-14% of the total weight of the fiber. The present invention further discloses a method for preparing a highly cut-resistant ultrahigh molecular weight polyethylene fiber, comprising: adding nanocrystalline silicon carbide particles to a solvent, and repeatedly grinding by a sand mill; adding a ultrahigh molecular weight polyethylene, and the silicon carbide nanoparticles to a solvent, and mixing until uniform by stirring by a homogenizer with high shear, to obtain a spinning solution; and subjecting the spinning solution to conventional gelation spinning, and extracting and hot drawing the gel filament spun, to obtain a composite fiber. In the present invention, by introducing the nanocrystalline ultrafine particles into the ultrahigh molecular weight polyethylene fiber, the composite fiber of ultrahigh molecular weight polyethylene/nanocrystalline ultrafine particles has a quite excellent cut-resistant performance.

Claims

1. A highly cut-resistant ultrahigh molecular weight polyethylene fiber, comprising ultrahigh molecular weight polyethylene and an inorganic ultrafine micropowder having a nanocrystalline structural morphology, wherein the inorganic ultrafine micropowder is one of an oxide, carbide, and nitride of aluminium, titanium, silicon, boron, and zirconium, or a combination thereof, and the inorganic ultrafine micropowder has an average diameter of 0.1-300 m and a content of 0.1-14% of the total weight of the fiber, the inorganic ultrafine micropowder is dispersed within the polyethylene fiber, wherein the inorganic ultrafine micropowder comprises nanocrystalline silicon carbide particles and one-dimensional nano-wire, nanorod, or nanobelt distribution of several nanometers in thickness attached on a surface of the nanocrystalline silicon carbide particles, wherein the nanocystalline silicon carbide particles comprise silicon-carbon bonds, and the one-dimensional nano-wire, nanorod, or nanobelt distribution of several nanometers in thickness comprises silicon-oxygen bonds; wherein a proportion of the silicon-oxygen bonds to the silicon-carbon bonds ranges from 0.1:1 to 0.5:1 when the inorganic ultrafine micropowder is detected by X-ray photoelectron spectroscopy (XPS).

2. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 1, wherein the inorganic ultrafine micropowder has a nanocrystalline structure that is of a hexagonal, tetragonal, or polygonal crystalline form, and has a percentage of total crystallinity that is greater than 95%.

3. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 1, wherein the ultrahigh molecular weight polyethylene fiber has a tensile strength of 17-23 cN/dtex and a tensile modulus of 700-900 cN/dtex.

4. A method for preparing the highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 1, comprising the steps of: (1) using a nanocrystalline silicon carbide micropowder as an inorganic ultrafine micropowder, wherein a 2-5 nm thick surface layer of the nanocrystalline silicon carbide particles has a silicon-oxygen chemical bonding pattern via a number of silicon-oxygen bonds Si2p-O, the ratio [Si2p-O/Si2p-C] of this pattern to the bonding pattern via silicon-carbon bonds Si2p-C is 0.24, and the value is calculated by Formula (1): [Si2pO/Si2pC]=ISi-o/ISi-c; (2) dispersing the nanocrystalline silicon carbide particles and a dispersing agent in a ultrahigh molecular weight polyethylene powder by high-shear blending; (3) ultrasonically dispersing a powder premix prepared with 88-99.5 parts by weight of the ultrahigh molecular weight polyethylene and 0.5-12 parts by weight of the silicon carbide nanoparticles uniformly into a solvent at a certain ratio, and mixing until uniform by stirring for 2-4 hrs by a homogenizer with high shear at a speed of 1000-3000 r/min, to obtain a 6-8.5 wt % spinning solution; and (4) subjecting the spinning solution to gelation spinning at a temperature of 230-280 C., and extracting and hot drawing the gel filament spun after the step of spinning, to obtain a composite fiber.

5. The method for preparing the highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 4, wherein the ultrahigh molecular weight polyethylene has a molecular weight of 410.sup.6 g/mol-810.sup.6 g/mol.

6. The method for preparing the highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 4, wherein the silicon carbide nanoparticles have an average diameter of 0.1-300 m.

7. The method for preparing the highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 4, wherein the solvent is one or more of white oil, paraffin oil, decalin, and mineral oil, and has a viscosity of 40-100 Cst at 40 C.

8. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 1, wherein the highly cut-resistant ultrahigh molecular weight polyethylene fiber is included in a cut-resistant material.

9. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 8, wherein the cut-resistant material is included in cut-resistant gloves.

10. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 2, wherein the highly cut-resistant ultrahigh molecular weight polyethylene fiber is included in a cut-resistant material.

11. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 10, wherein the cut-resistant material is included in cut-resistant gloves.

12. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 3, wherein the highly cut-resistant ultrahigh molecular weight polyethylene fiber is included in a cut-resistant material.

13. The highly cut-resistant ultrahigh molecular weight polyethylene fiber according to claim 12, wherein the cut-resistant material is included in cut-resistant gloves.

Description

BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS

(1) FIG. 1 is a survey scan XPS spectrum of silicon carbide used in the present invention.

(2) FIG. 2 is a narrow scan spectrum of binding energy with a Si2p97.85 eV-105.55 eV broad peak of the element Si.

SPECIFIC EMBODIMENT

(3) The examples below are provided for merely illustrating, instead of limiting the protection scope of the present invention. The mechanical performance and thermal stability of the composite fiber prepared in example below are measured as follows in each case. The tensile strength and tensile modulus of the composite fiber are tested by a single fiber tensile strength and elongation tester, and the thermal stability in nitrogen is determined by thermogravemetric analysis.

Example 1

(4) 1) 1 g of a nanocrystalline silicon carbide powder with a particle diameter of 200 nm and a ratio [Si2p-O/Si2p-C] of surface element chemical bonding patterns of 0.24, and an dispersing agent Tween-80/SA=9/1 (HLB=13.5, 0.1 g) were dispersed in an ultrahigh molecular weight polyethylene powder by high shear blending. The prepared powder premix was ultrasonically uniformly dispersed in mineral oil, and then the solution in mineral oil (where the weight ratio of silicon carbide to UHMWPE was 1:99) was slowly heated in a reactor with stirring by shear at a speed controlled to 75-3000 r/min, until the solution was uniformly mixed.

(5) 2) Gelation spinning: A composite solution of UHMWPE/nano-silicon carbide well dissolved was spun by gelation spinning at a temperature of 240 C., and the prepared gel filament was extracted and drawn, to obtain the composite fiber of the present invention.

(6) The composite fiber prepared in the example has a nano-silicon carbide content of 1%, a tensile strength of 21 cN/dtex and a tensile modulus of 800 cN/dtex.

Example 2

(7) 1) 2 g of a nanocrystalline silicon carbide powder with a particle diameter of 200 nm and a ratio [Si2p-O/Si2p-C] of surface element chemical bonding patterns of 0.24 was dispersed in an ultrahigh molecular weight polyethylene powder by high shear blending. The prepared powder premix was ultrasonically uniformly dispersed in mineral oil, and then the solution in mineral oil (where the weight ratio of silicon carbide to UHMWPE was 2:98) was slowly heated in a reactor with stirring by shear at a speed controlled to 75-3000 r/min, until the solution was uniformly mixed.

(8) 2) Gelation spinning: A composite solution of UHMWPE/nano-silicon carbide well dissolved was spun by gelation spinning at a temperature of 240 C., and the prepared gel filament was extracted and drawn, to obtain the composite fiber of the present invention.

(9) The composite fiber prepared in the example has a nano-silicon carbide content of 2%, a tensile strength of 20 cN/dtex, and a tensile modulus of 810 cN/dtex.

Example 3

(10) Example 1 was repeated, except that the content of the nano-silicon carbide was 2 wt %, and the ratio [Si2p-O/Si2p-C] of element chemical bonding patterns on the surface of the nano-silicon carbide powder was 0.29.

Example 4

(11) Example 2 was repeated, except that the ratio [Si2p-O/Si2p-C] of element chemical bonding patterns on the surface of the nano-silicon carbide powder was 0.34.

Example 5

(12) Example 1 was repeated, except that the content of the nano-silicon carbide was 4 wt %, and the ratio [Si2p-O/Si2p-C] of element chemical bonding patterns on the surface of the nano-silicon carbide powder was 0.34.

Example 6

(13) Example 1 was repeated, except that the content of the nano-silicon carbide was 4 wt %.

Comparative Example A

(14) The components and the process were the same as those in Example 1, except that no nanocrystalline silicon carbide powder was added.

Comparative Example B

(15) Example 2 was repeated, except that the content of the nano-silicon carbide was 3 wt %, and the ratio [Si2p-O/Si2p-C] of element chemical bonding patterns on the surface of the nano-silicon carbide powder was 0.10.

Comparative Example C

(16) Example 2 was repeated, except that the content of the nano-silicon carbide was 4 wt %, and the ratio [Si2p-O/Si2p-C] of element chemical bonding patterns on the surface of the nano-silicon carbide powder was 0.60.

(17) Use of the highly cut-resistant ultrahigh molecular weight polyethylene fiber as a cut-resistant material is provided below.

(18) A method for producing cut-resistant gloves containing the composite fibers above includes cladding polyurethane filaments with a fiber cladding material and high-strength polyethylene fibers, where the fiber cladding material and the high-strength polyethylene fibers are clad respectively outside the polyurethane filaments in a forward and reverse direction.

(19) The produced gloves have a reasonable structure, a high strength, and a high cut resistance, and achieves level 5 of protection authenticated internationally.

(20) In the examples, the method for determining and evaluating the principal control data includes the following.

(21) As exemplary detection and quantitative evaluation, the ratio [Si2p-O/Si2p-C] of two chemical bonding patterns of the element silicon in the surface layer of the nanocrystalline silicon carbide powder is determined by X-ray photoelectron spectroscopy (XPS).

(22) The instrument used and conditions set: XPS Model (UK) Thermo ESCALAB 250.

(23) Excitation source of X ray: monochromatic source Al Ka (hv=1486.6 eV); power 150 W, X-ray beam spot 500 m;

(24) Fixed transmitted energy of energy analyzer: 30 eV, scanning range: 0-1200 eV.

(25) X-ray photoelectron spectroscopy (XPS) is based on the fact that the surface layer of a sample material is irradiated with a monochromatic X-ray source or electron beam, such that the electrons of the element atoms in the surface layer are excited to be emitted, and information of materials that are about several nanometers deep in the surface can be obtained by detecting the energy distribution and intensity of the excited electrons that are mainly associated with the electron orbit binding energy, whereby the species, state and relative content of the elements existing in the surface of the nano-silicon carbide powder can be qualitatively or quantitatively detected.

(26) FIG. 1 is a survey scan XPS spectrum of silicon carbide used in the present invention. During the analysis of each peak in the spectrum and the analysis and calculation of the species, state and relative content of the elements existing in the surface of the nano-silicon carbide powder, the carbon peak C(1s)282.7 eV is used as an internal standard, and the remaining peaks are Si2p 100.62 eV, O1s 532.14 eV, Ca2p347.98 eV, Fe2p712.08 eV, and Na1s1072.65 eV.

(27) FIG. 2 is a narrow scan spectrum of binding energy with a Si2p97.85 eV-105.55 eV broad peak of the element Si, showing that the Si2p peak of the element silicon of two chemical bonding patterns is split into doublet peaks A and B, the binding energy of 100.6 eV and 102.5 eV correspond respectively to SiC and SiO, the Si2p photoelectron binding energy of the later bond is increased by shifting 1.9 eV to a high binding energy, the Si2p photoelectron peak is two single Gaussian peaks (with Gaussian distribution) that are partially overlapped, and the intensity may be obtained through integration of the two peaks, which may be implemented by a computer. Assuming that the peak intensities (the area integrated is A and B respectively) of the binding energy (A) Si2p100.6 eV and (B) Si2p102.5 eV are ISi-c, and ISi-o separately, the relative level of the chemical bonding patterns of the element in the surface of the nanocrystalline silicon carbide powder can be calculated by a formula below:
[Si2p-O/Si2p-C]=ISi-o/ISi-c=B/A(1)
Cut-Resistance Test of Product

(28) The test was conducted according to the national standard GB24541-2009 or the European standard EN388. According to the European standard EN388, a cut resistance tester was used to test the cut resistance of protofilaments (gloves), in which the apparatus was a tester manufactured by Sodemat according to the European standard EN388. The sample was positioned on a work bench of the cut resistance tester, below which an aluminium foil was padded and moved horizontally. A circular blade was rotated against the sample while advancing in a direction (at 180 with respect to) opposite to the movement direction of the sample. At the time point when the sample was completely cut off, the circuit blade was in contact with the padded aluminium foil and electrified, whereupon the circuit notified the counter of the termination of cutting. Throughout the whole process, the counter was persistently kept recording. As such, the cut resistance of the sample was obtained.

(29) After test, the level of cut resistance was evaluated through comparison with that of a standard sample (that was a planar cotton fabric of 200 g/m2) tested under the same conditions. The test was started with the standard sample, and the cut test was conducted alternatively with the test sample and the standard sample. After the third test with the test sample, the fourth test with the standard sample was conducted, and then this round of test was ended.

(30) A value is calculated according to a formula below, which is designated as cut resistance index:

(31) N=(reading of the counter for the standard sample before the test of the test sample+reading of the counter for the standard sample after the test of the test sample)/2; Index=(reading of the counter for the test sample+N)/N

(32) The level is scaled according to the index:

(33) TABLE-US-00001 Index Level of cut resistance 2.0-2.5 1 2.5-5.0 2 5.0-10 3 10.0-20.0 4 >20 5

(34) In addition, the circular blade used in the test is an L-type rotary cutter blade manufactured by OLFA having a diameter of 45 mm (which is made from SKS-7 tungsten steel, and has a thickness of 0.3 mm).

(35) The table below shows test results of the fibers from the examples and comparative examples

(36) TABLE-US-00002 Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example A Example B Example C Content 1 2 2 2 4 4 0 3 4 of nanocrystalline SiC particles, % B/A ratio 0.24 0.24 0.29 0.34 0.34 0.24 0.10 0.60 of bonding patterns in the surface of SiC Tensile 21 20 20.5 21 19.5 19 25 20.5 21 strength, cN/dtex Tensile 800 810 810 810 820 820 900 820 820 modulus, cN/dtex Level of 4-5 5 5 5 5 5 2 3-4 4-5 cut resistance (end product)

APPLICABILITY OF THE PRESENT INVENTION IN INDUSTRY

(37) The ultrahigh molecular weight polyethylene fiber of the present invention and the braided gloves containing the fibers etc have excellent cut resistance and anti-abrasion performance, and have a high post processing passing rate and an increased productivity, thus being useful in various areas having high and strict requirement for protection performance (for example, sports, aviation, marine navigation, mining, oceanographic engineering, various military and civilian facilities, clothes, hats, gloves and footmuff), and contributing a lot to the industrial development and economic benefits.