Accepted Manuscript

Investigation of structure, mechanical and tribological properties of short carbon fiber

reinforced UHMWPE-matrix composites

D.I. Chukov, A.A. Stepashkin, A.V. Maksimkin, V.V. Tcherdyntsev, S.D. Kaloshkin,
K.V. Kuskov, V.I. Bugakov

PII: S1359-8368(15)00105-5
DOI: 10.1016/j.compositesb.2015.02.019
Reference: JCOMB 3420

To appear in: Composites Part B

Received Date: 2 September 2014

Revised Date: 6 February 2015
Accepted Date: 13 February 2015

Please cite this article as: Chukov DI, Stepashkin AA, Maksimkin AV, Tcherdyntsev VV, Kaloshkin
SD, Kuskov KV, Bugakov VI, Investigation of structure, mechanical and tribological properties of
short carbon fiber reinforced UHMWPE-matrix composites, Composites Part B (2015), doi: 10.1016/
j.compositesb.2015.02.019.

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 ACCEPTED MANUSCRIPT

Investigation of structure, mechanical and tribological

properties of short carbon fiber reinforced UHMWPE-matrix

composites.

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D.I. Chukova, A.A. Stepashkina, A.V. Maksimkina, V.V.

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Tcherdyntseva, S.D. Kaloshkina, K.V. Kuskova, V.I. Bugakovb

a) National University of Science and Technology “MISIS”, 119049 Moscow, Russia

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b) Institute for High Pressure Physics Russian Academy of Sciences, 42190, Troitsk,

Moscow, Russia

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Corresponding author: D.I. Chukov, Leninskiy pr. 4, 119049 Moscow, Russia

e-mail: dil_chukov@yahoo.com. +7 (903) 269 03 43

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Abstract
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Structural, mechanical and tribological properties of composite materials based

on ultra-high molecular weight polyethylene reinforced with carbon fibers were

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investigated. The effect of surface modification of carbon fibers on the interaction at the

fiber - matrix interface in UHMWPE based composites was studied. It was found that
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the thermal oxidation of carbon fibers by air oxygen at 500 ºC can significantly enhance
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the interfacial interaction between the polymer matrix and carbon fibers. This allowed

us to form composite materials with improved mechanical and tribological properties.

Keywords

A. Carbon fibre; A. Polymer-matrix composites (PMCs); B. Fibre/matrix bond;

B. Mechanical properties; UHMWPE

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1. Introduction

Wide application of polymer composites is associated with their advantages over

traditional materials, such as a possibility to obtain a required combination of

properties, which cannot be achieved for unfilled polymers. The ability to control the

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properties of composites over a wide range by adjusting the reinforcing elements and

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changing the degree of filling is the reason for increased interest in composite materials.

Ultra-high molecular weight polyethylene (UHMWPE) is one of promising

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matrix materials due to its high wear resistance, low friction coefficient, high chemical

resistance, bioinertness. At the same time, UHMWPE has some disadvantages such as

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low hardness and Young’s modulus and a high creep rate under a load, which
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significantly limit its application [1]. For example, UHMWPE is currently the most

often polymer used in the orthopaedic prostheses, such as acetabular cup component of
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the total hip replacement, but it has also found an extensive use as a bearing surface in

knee, ankle, shoulder and as a prosthetic cruciate ligament [2,3]. Many problems with
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this polymer implants originate from its low creep resistance compared with the metal
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stem and cortical bone in the replaced hip joint system [4].

One way to improve the mechanical properties of this polymer is reinforcing it

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with disperse particles [5-8]. Various materials are used as fillers for polyethylene to

change its functional properties. Carbon-based fillers, such as carbon black, graphite
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powder, carbon nanotubes are most often used to improve its electrical and thermal
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properties [9-13]. Solid lubricants, such as glass, kaolin, Al2O3, and molybdenum

disulfide (MoS2) have been evaluated with UHMWPE for improved tribological

properties of composites [14-16]. However, the use of such fillers not always enables

one to achieve high mechanical properties such as high tensile strength, Young

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modulus, yield strength etc. of the composites. An alternative approach may be the use

of fibrous fillers as the reinforcing elements. Carbon, basalt, aramid, wollastonite and

glass fibers were used as the fillers for the UHMWPE-based composites [17-20]. In our

study, we use carbon fibers (CF) due to their high tensile strength and elastic modulus;

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in addition, in many cases, the reinforcement of polymers with carbon fibers can

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significantly improve the tribological and thermal properties of the composites [21-24].

The application of carbon fibers is very limited, mainly, due to their high cost.

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However, the composites reinforced with short (with an average length of less than 10

mm) CF can be formed of the recycled CF or can be recovered from the composite

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materials based on thermosetting polymers. These fibers are much cheaper than the
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initial CF and can be used to reinforce thermoplastic polymers, in particular UHMWPE,

in order to improve their physical, mechanical, tribological, thermal, and electrical

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properties [25-27].

A high molecular weight of UHMWPE (up to 107 g/mol), which determines its
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unique properties, simultaneously imposes the limitations on its processing. This is due
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to the fact that polyethylene with a molecular weight less than 5*105 g/mol, at the

temperatures above the melt temperature, can undergo a flow transition and become
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liquid. However, at a molecular weight above 5*105 g/mol, the entanglement of the

polymer chains prevents it from flowing [1], and a high melt viscosity of UHMWPE
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does not allow mixing it with fillers in the molten state, as it is commonly performed
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with the low molecular weight polymers. Therefore, the traditional polymer processing

methods, such as extrusion and injection molding, are almost inapplicable. One possible

way of solving this problem is to obtain solutions of UHMWPE, to mix the solution

with the fillers, and, then, to remove the solvent [28,29]. However, the application of

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this method for introduction of macroscale fillers, such as short fibers, into the polymer

is complicated by their large length. Moreover, this technology is high labor consuming

and requires the use of toxic solvents (xylene, decalin, and paraffin oil) [30-32].

The methods of solid phase synthesis of composite powders are widely used for

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producing polymer matrix composite materials. It was found that high energy ball

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milling leads to uniform distribution of the filler in the polymer matrix and a high

adhesion of the filler to the matrix [33-35]. On the other hand, the mechanical milling

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leads to decrease of polymers particle sizes, and, in some cases, may be accompanied by

rupture of polymer chains, transformation of amorphous and crystalline phases and

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formation of oriented amorphous regions [36, 37]. The main drawback of mixing in a
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planetary mill is its applicability to only some types of fillers (powders, granules). In the

case of fibrous fillers, such as carbon fibers, which are very unstable to impact loads,
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the use of high-energy ball mills can lead to the mechanical destruction of fibers.

According to the calculations for the UHMWPE-carbon fibers system [38], at a fiber
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length less than 0.8 mm, they lose their reinforcing ability; under a load the fibers are
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pull-out from the matrix, and the generated pores can serve as stress concentrators and

the crack nuclei. Therefore, in order to reach high mechanical properties of short fibers
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reinforced composites, it is necessary to control the length of the reinforcing fibers. This

is impossible in the case of planetary mills due to uncontrolled destruction of fibers.

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A serious problem in developing carbon fibers reinforced UHMWPE matrix

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composites is their chemical inertness and, as a consequence, poor interfacial interaction

between the fibers and polymer matrix. Earlier [39, 40] it was shown that a strong

interfacial interaction between UHMWPE and CF may be achieved only after the

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surface modification of carbon fibers. Therefore, surface modification of CF is of

importance for achieving high mechanical properties of the composites.

The goal of the present work is to study the effect of the reinforcement of

UHMWPE with short carbon fibers on the mechanical and tribological properties of

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composites. Currently widely used material for tribological application is

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polytetrafluoroethylene (PTFE) and composite materials based on PTFE filled with

disperse graphite particles. Using UHMWPE as a matrix material may allows to

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produce composite materials with improved functional properties capable of operating

in aggressive environments and high loads over a wide temperature range: from

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cryogenic up to + 100 °C. The developed materials can be successfully applied in
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friction units which work without lubrication. They can work in vacuum and in dried

gases (the sealing ring of compressors), as well as in wet gases and in various liquids.
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As applications of these materials may be the production of inserts of axial and radial

sliding bearings, piston rings etc.

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Advantages of UHMWPE-based composites is that they have a substantially

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lower density than materials based on PTFE which allows to reduce weight of products.

The use of carbon fibers as fillers allows to produces composite materials with higher
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mechanical properties than in case of filling with graphite particles. The disadvantages

of the developed materials should include a more narrow temperature range of their use
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due to the lower thermal resistance of UHMWPE as compared to PTFE, which should
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be considered when choosing the working conditions of materials.

2. Experimental

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The GUR 4120 UHMWPE powder (Ticona, Germany) with a molecular weight

of 5*106 g/mol and an average particle size of 120 µm was used as the matrix material.

High-strength UKN 5000 carbon fibers (OOO “Argon”, Russia) with an average tensile

strength of 4 GPa and elasticity modulus of 250 GPa were used as the filler. The content

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of carbon fibers in the composites varied from 0 to 12wt.% and their average length

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achieved after processing the material was about 1 mm.

The surface modification of carbon fibers was carried out by the chemical and

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thermal oxidation. The chemical oxidation of the fiber surface was performed by the

direct action of 68.3% nitric acid (HNO3) for 1–72 h at 25º C. The oxidized fibers were

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washed with distilled water and dried at 80º C for 6 h. The thermal oxidation of carbon
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fiber was carried out in the air atmosphere at the temperatures of 100–500º C for 10–60

min.
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The UHMWPE - carbon fibers composite powders were formed by using

UHMWPE powder, which was milled in a planetary mill for 60 minutes. Ball milling
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was carried out in an APF-3 high-energy planetary mill in steel vials; steel balls with a
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diameter of 10 mm were used as the grinding media. The carrier’s rotation speed was

constant and equal to 400 rpm. A preliminary milling was carried out in order to change
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the morphology of the initially spherical particles to the lamellar shape.

The solid phase method, which involves the codeformation processing of

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polymer and reinforcing fillers with the use of an IKA M20 laboratory mill, was applied
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for fabrication of composite powders. The processing duration was adjusted

experimentally depending on the required length of carbon fibers and their uniform

distribution over the entire volume of composite powder. These parameters were

controlled by taking samples during the milling and investigating them with a scanning

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electron microscope. The required length of carbon fibers (1 mm) was achieved after 1

min of processing.

The bulk samples of composite materials were produced by compression molding

at a temperature of 160º C, and a pressure of 60 MPa. The phase composition and

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crystalline structure of the powders were studied by the X-ray diffraction analysis with a

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Rigaku Ultima IV diffractometer using Co Kα radiation. The structure of initial

components and fiber-reinforced composites was investigated with a Jeol JSM 6610LV

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scanning electron microscope in the secondary electron image mode and a Hitachi TM-

1000 low-vacuum scanning electron microscope in backscattered electron image mode.

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The tensile and compression tests of composites were carried out on a Zwick Z020
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universal testing machine at a speed of 10 mm/min. For the tensile tests, the samples 80

mm in length, 10 mm in width and 2 mm in thickness were used; for the compression

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test, cylindrical samples 10 mm in diameter and 20 mm in height were used; the

compression creep tests were carried out on the same cylindrical samples at a normal
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stress of 5 MPa and 10 MPa, the test duration was 200 min.
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. The wear rates and friction coefficients of the composites were measured with a

CETR-UMT-3 tribometer. The tribological tests were carried out in a pin-on-disc

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friction mode with distilled water lubrication on the composite pins 6.3 mm diameter

and 10 mm in height; samples were loaded against stainless steel (Ra=0.35 ±0.005 µm),
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a normal contact load was 100 N, a disc rotation speed was 100 rpm (a linear speed of
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0.25 m/s); the test duration was 2 hours. Wear was measured as the difference between

the height of the sample before and after the test, which was recorded automatically by

tribometer.

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3. Results and discussion

In the initial state, the UHMWPE particles are spherical with an average size of

120 microns (Fig. 1a). The UHMWPE - CF composite powders were obtained by using

the UHMWPE powder, which was milled in a planetary mill for 60 minutes (Fig. 1b).

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The preliminary treatment of UHMWPE is caused by the fact that the application of the

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source UHMWPE powder leads to the stratification of composite powder during

transportation, storage and subsequent processing steps, i.e. the UHMWPE particles

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settle down while the fibers remain on top. As a result, inhomogeneous composite

powder is formed.

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[ approximately Figure 1.]
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During the ball milling, the morphology of UHMWPE particles changes: initially
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spherical particles acquire a lamellar shape, and their size doubles up to 250 µm. This

change of morphology enabled us to obtain and maintain a more homogeneous

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composite powder with uniform distribution of carbon fibers over the entire volume;
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even after a long-term storage, no stratification of composite powder was observed. The

morphology changes of the UHMWPE particles allow to obtain closer mechanical

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contact between the UHMWPE and CF and the change in the surface roughness of the

UHMWPE particles increases the mechanical engagement between components of

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composites, which results in reduced stratification.

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According to the results of X-ray analysis (fig. 2) polyethylene is the

semicrystalline polymer, which consists of an amorphous phase and an orthorhombic

crystalline phase with two intensive peaks at 24.95° (110) and 27.7° (200) (Fig.2). It is

known that under the influence of intense shear and compressive loads on the

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UHMWPE powder, a phase transition from orthorhombic to monoclinic phase can

occur [41]. From Fig. 2, it can be seen that ball milling of UHMWPE leads to the

formation of a new peak at 2θ = 22.9°, which corresponds to the monoclinic phase. At

the same time, the (200) peak broadens, which can be associated with a decrease in

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crystals size or with the formation of some defects on their surfaces.

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[ approximately Figure 2.]

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The deformation prehistory of UHMWPE predetermined by ball milling is

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blended after compression molding. After the heating of the powder above the melting
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point, the monoclinic phase, which is metastable [42, 43], is transformed back into a

more stable orthorhombic phase and, due to the shape memory effect, which is inherent
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to UHMWPE [44], the powder particles regained their initial spherical shape (Fig. 3).

Moreover, it was shown [41] that heating UHMWPE after ball-milling above the
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melting point leads to an almost complete return to the initial mechatical properties and
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changes in the structure of UHMWPE are reversible and disappear when it heated above

the melting point. No other notable structural changes, which could affect the properties
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of the composites, were observed, therefore, the use of ball–milled powder instead of

the initial UHMWPE in our case is justified only in relation to the uniformity of
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distribution of the fibers over the entire volume of the composites.

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[ approximately Figure 3.]

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The stress distribution in short fiber composites using equilibrium of forces

acting on an isolated fiber, the normal stress at any distance x from either end of the

fiber can be written as

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4 x
σf = ∫ τ dx i (1)

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df 0

where σf = normal stress in the fiber, τi = interfacial shear stress, df = fiber diameter.

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[45].

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Assuming that the interfacial shear stress τi is constant (which is an
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simplification), rewrite Equation (1) as follows
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4τ i
σf = x
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df (2)
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According to Equation (2), the normal stress in the fiber increases linearly from

zero at each end (i.e., at x=0). If the maximum normal stress equals the fiber tensile
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strength, the fiber will break. The minimum length required for the maximum normal

stress in the fiber to become equal to the fiber tensile strength is called the critical fiber
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length (lcr) From Equation (2), the critical fiber length lcr is obtained as
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σ ts
lcr = df
2τ i (3)

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where σts = tensile strength of the fibers.

If the fiber length lf is less than the critical length lc, the maximum fiber stress

will not reach the fiber tensile strength and the fiber will not break in tension. In this

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case, failure in the composite is initiated either by interfacial bond failure or matrix

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cracking. On the other hand, if the fiber length is greater than the critical length fiber

will break in tension, what allows more effective use of the fibers. In the case of

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thermoplastic polymers maximum interfacial shear stress τi is limited by yield strength

of polymer matrices, so it is convenient to use it to calculations. According to the

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calculations, the the critical length of the carbon fibers fibers lcr in UHMWPE-matrix
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which is required for reaching the reinforcing effect should be 1 mm.

Fig. 4 shows the results of scanning electron microscopy study of the composite
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powders after milling in an IKA mill. At low processing times (30 seconds), an average

fiber length was significantly larger than the critical length, i.e. no considerable
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destruction of CF at milling was observed. However, the distribution of fibers over the
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entire volume was not uniform, and for better distribution, longer processing times were

required. It was found that 1 min was the optimal processing time, which provided a
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uniform distribution of the fibers and the desired average fiber length of ~ 1 mm or
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more.
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[ approximately Figure 4.]

An increase in the milling time to 2 minutes leads to the destruction of carbon

fibers. On the micrographs, fibers with the length of 500 microns or less are observed,

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i.e. their length becomes less than the critical value, and, therefore, their reinforcing

effect on the composites will hardly occur. Therefore, the composite powder after

milling for 1 min was used to obtain the bulk samples. Further low magnification SEM

images showing the distribution of the fibers along the matrix after 1 minutes milling

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time are shown in Fig.5. In both cases on the surface of UHMWPE reinforced with 8

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wt.% carbon fibers after tensile tests (Fig.5(a)) and on the quasibrittle fracture surface

(Fig.5(b)) is observed uniform distribution of carbon fibers by volume of the matrix

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material.

[ approximately Figure 5.]

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The surface of the carbon fibers at the initial state is chemically inert. Therefore,

the interaction at the polymer matrix – fibers interface is almost absent. This leads to a
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low load transfer from UHMWPE to CF, which has a negative effect on the mechanical

properties of the composites. The modification of the fiber surface is the most efficient
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method to improve the interfacial interaction with the polymer matrix [46-48]. During
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the oxidation treatment of carbon fibers, loosely bonded defective surface layer of

carbon is removed, the oxygen chemisorption proceeds, oxygenated functional groups

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capable of reacting with the polymer matrix form on the edge carbon atoms, and, hence,

the required interfacial strength in the composites is reached. Depending on the

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processing conditions, the structure and surface morphology of carbon fibers may
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undergo considerable changes.

[ approximately Figure 6.]

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At the initial state, the surface of the UKN-5000 carbon fibers is coated with a

film of a coupling agent (Fig. 6). It is seen that the film was applied nonuniformly, and

sinters on the fibers surface are observed. Our preliminary studies showed that the

presence of epoxy coupling agent on the CF surface prevents the interfacial interaction

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between UHMWPE and CF, which plays a role of separation layer. Its removal is

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required in order to obtain high mechanical properties of UHMWPE based composites.

The methods of thermal and chemical oxidation not only enable one to remove the

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coupling agent layer, but also have a strong affect on the surface morphology of fibers.

For example, after chemical modification of UKN-5000 fibers in nitric acid for 72

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hours, rather deep etch grooves along the fibers axis are seen on the fibers surface. They
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form as a result of removal of amorphous carbon and defective layer from the boundary

of the fibril, which form carbon fibers. In addition, the delimitation of ribbon-like fibrils
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0.2-0.7 µm in width starts (Fig. 7a, 7b).
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[ approximately Figure 7.]

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During the thermal oxidation at a temperature of 500 ºC for 10 minutes, the

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oxidation progress inward, which leads to the formation of well-developed surface with

the craters smaller than 1 µm in diameter (Fig. 7c, 7d). In this case, the oxidation of
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both amorphous carbon and more stable carbon structures occur. Thus, the thermal
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oxidation has a stronger effect on the fibers structure than the chemical oxidation.

The micrographs of the fractures of UHMWPE based composites enable us to

estimate the effect of surface modification on the interfacial interaction between the

fibers and the polymer matrix.

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It can be seen that, in the case of reinforcing with untreated fibers, no

sufficiently strong bonds between the matrix and unmodified fibers form. Only at the

end faces of the fibers, the edge carbon atoms with unsaturated bonds show the ability

to react with the polymer.

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[ approximately Figure 8.]

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Thermal oxidation of carbon fibers leads to strong interfacial interaction

between CF and UHMWPE (Figs. 8c and 8d). The fractographic analysis of composites

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showed the formation of UHMWPE nanofibrils on the fibers surface, which is the
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evidence for the formation of chemical bonds between the UHMWPE and active

functional groups on the carbon fiber surface. At the same time, it is clearly seen, that
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individual filaments can be coated with a thin continuous film of the polymer (Fig. 8d),

which is a source material for the formation of nanofibrillar structure on the carbon fiber
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surface.
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The Young's modulus of the composites reinforced with carbon fibers at the

initial state and after thermal oxidation at 500 °C for 10 minutes (Fig. 9) can be used as
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a criterion of effectiveness of CF surface treatment. It can be seen that reinforcing with

non-treated fibers leads to an increase in the Young’s modulus with increasing fibers
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content from 0.75±0,05 GPa for pure, unfilled UHMWPE to 1.54±0,03 GPa at 10 wt %
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carbon fibers. In the case of modified fibers, at 2 wt % CF, the Young’s modulus is

1.56±0,08 GPa and, at 10 wt % carbon fibers, it reaches 4.1±0,06 GPa.

[ approximately Figure 9.]

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The introduction of carbon fibers in UHMWPE has almost no effect on the plasticity of

the composites which have a ductile fracture mode. Elongation at break of carbon fiber

reinforced composites close to the value of pure UHMWPE (390±30%). Preservation

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high ductility of composites in the presence of brittle carbon fibers, (elongation at break

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less than 1%) associated with “joint work” of the fibers and polymer matrix only at low

deformations. This is further supported by the fact that, despite more than a fivefold

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increase in the Young’s modulus, increase the tensile strength of the composites is no

observed. This is due to the fact that the increase in tensile stress leads to deformation of

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the polymer matrix, and under load the "cells" that include carbon fibers and
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macrovolume of polymer slide against each other. Such deformation behavior leads to

the fact that fracture occurs in the volume of the matrix material rather than at the fiber -
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matrix interface of the composites. Therefore, even after the destruction of composites,

the carbon fibers with a layer of the polymer matrix are observed.
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The results of compression tests of UHMWPE-based composite materials with

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different thermal oxidized CF content are shown in Fig. 10. Yield stress σ0.2 of

composites increases monotonically with increasing carbon fibers content. There value
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of σ0.2 increases almost twofold from 11.6±1.1 MPa for the initial UHMWP to 20.5±1

MPa for the composite reinforced with 12 wt % CF. The Young's modulus of the
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composites also increases to the yield stress with increasing content of CF. The
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maximum value of 2170±110 MPa, as well as is the case of σ0.2, is observed at the

maximum content of CF (12 wt %) in the composites.

[ approximately Figure 10.]

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A significant disadvantage of UHMWPE, like most of thermoplastic polymers,

is a strong deformation under a load. Low creep resistance in the long service can cause

a failure of UHMWPE products due to uncontrolled plastic deformation under static

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loads. The strain versus time curves of initial UHMWPE and its composites are shown

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in Fig. 11. The creep behavior is similar for all test materials: at the first stage, the creep

is characterized by relatively high-rate plastic deformation. At this stage, the creep

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resistance increases leading to a decrease in the deformation rate, it’s so called transient

creep. At the second stage, the deformation rate is constant and relatively low, which

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corresponds to the linear curve portion (the steady-state creep). Strain of unfilled
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UHMWPE by the end of the test at a stress of 5 MPa was 1.13±0.01% (Fig. 11a). The

introduction of carbon fibers into UHMWPE increases the creep resistance. There is a
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clear correlation between the strain rate and the degree of filling with carbon fibers; an

increase of CF content leads to a decrease of strain rate. The best results were obtained
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for a composite with the maximum CF content, i.e. reinforced with 12 wt % CF, its
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strain was 0.74±0.03%, which is 1.5 times less than that for initial UHMWPE.

A twofold increase of applied stress (up to 10 MPa) leads to an increase in the

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strain rate of all specimens (Fig. 11b). For the initial UHMWPE, the maximum strain

was 3.18±0.02%, which is almost three times higher than at 5 MPa. At the same time,
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for the composites, the strains increased by 2.2-2.5 times (when the load increased from
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5 to 10 MPa) depending on the degree of filling. An increase of applied stress had no

effect on the creep behavior of the composites: as well as in the first case, the creep

resistance increased with increasing content of carbon fibers, and the minimum value of

strain (1.74±0.03%) is observed for a composite reinforced with 12 wt % CF.

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[ approximately Figure 12.]

The analysis of creep behavior of CF reinforced composites suggests three main

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factors, which lead to a significant increase in the creep resistance. The first factor is the

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presence of a rigid net (skeleton) formed by CF, which is not prone to creep. This is

supported by a considerable increase of the yield stress of the composites as compared

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with the initial UHMWPE. The second factor is the volume effect: a relative volume of

viscoelastic polymer matrix, which is prone to creep, is smaller in the composites. The

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third factor is the blocking effect: the additives interact with the molecular chains of
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polymer matrix and prevent them from moving under the stress. Obviously, the effect of

the first two factors is predominant in the case of fiber-reinforced composites, because a
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relatively small fraction of polymer chains directly interact with the fibers.

Fig 12 shows friction coefficients and wear values of composites under water
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lubricated conditions. Standard deviation of friction coefficients and wear values was
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about 0.002 and 5 µm, respectively. Fig. 12a shows the time dependence of the friction

coefficient µ for the initial UHMWPE and for the composite reinforced with 12 wt %
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CF.
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[ approximately Figure 12.]

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The initial value of the friction coefficient for UHMWPE is 0.13, the minimum value of

0.07, which is reached after 27 min. This may be a result of the formation of transfer

film on the counterface surface, which is typical for UHMWPE and UHMWPE-based

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composites [49-51]. Then, µ increases up to 0.09 by the end of the test. The observed

increase of friction coefficient, probably, is due to an increase of temperature in the

contact of the counterface and the test sample. The initial friction coefficient of the

composite material reinforced with 12 wt % CF is lower than that for initial UHMWPE

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(µ = 0.12). The friction coefficient of the composite is more stable with the time. By the

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end of the test, it reaches the minimum value of 0.07. Less stable behavior of friction

coefficient of the initial UHMWPE as compared with the composites is associated with

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the higher thermal conductivity of the composites, which causes a better heat removal in

the contact zone. It was shown that the time dependences of friction coefficient for the

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composites with lower carbon fibers contents were similar.
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The wear of initial UHMWPE after two-hour test was 225 µm (Fig. 12b). The

reinforcement with carbon fibers can significantly reduce the wear. The lowest wear of
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110 µm was obtained for a composite with 8 wt % CF. However, further increase of CF

content to 12 wt % reduces the wear resistance of the composite; this is caused by a

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partial "chipping" of carbon fibers from the friction surface. It could also be due to a
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lack of homogeneity of the composites with increasing of the carbon fibers content

because at higher contents carbon fibers tend to agglomerate, and accordingly, their bad
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distribution by the entire volume of polymer matrix may observed. However, the wear

of the composites remained lower than the wear of the initial polymer. It should be
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noted that the highest intensity of wear of composites was observed at the initial stage,
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the so-called alignment; then, wear rate significantly decreased. A lower wear of carbon

fibers reinforced composites as compared with UHMWPE is due to a possible change in

the mechanism of wear from adhesive to the fatigue wear [52].

4. Conclusions

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1) A method of solid-phase synthesis of the composite materials based on

UHMWPE, which are reinforced with carbon fibers, was proposed. The method enables

us to obtain uniform distribution of carbon fibers and required average fiber length. It

was shown that the ball milling for 1 hour changes the morphology of the UHMWPE

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powder particles and increases the particle size. The use of the ball–milled powder

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instead of initial UHMWPE provided more uniform distribution of fibers within the

entire volume of matrix material and prevents the separation of fibers from UHMWPE

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in the composite powder in the course of further technological operations. In addition

the composite powder should be treated in a IKA M20 mill for 1 min in order to obtain

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a uniform distribution of the fibers and an average fiber length of ~ 1 mm or more.
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2) The optimal modes of chemical and thermal surface modification of carbon

fibers were determined. It was shown that the oxidation by nitric acid leads to removes
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amorphous carbon and defective layer from the boundary of the fibril, which form

carbon fibers. The air oxidation leads to the formation of well-developed fiber surface
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with a system of craters. The optimal oxidation temperature was 500 °C.
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3) Scanning electron microscopy studies of structure of carbon fiber reinforced

composite showed that the optimal interfacial interaction between the CF and
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UHMWPE with the form a continuous polymer film on the fibers surface is realized

after the thermal oxidation of fibers at 500 °C. The Young's modulus of composites
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reinforced with modified fibers is significantly higher than in the case of unmodified
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fibers and is 5 times higher than that of initial UHMWPE.

4) The yield stress of composites at compression tests is almost two times higher

than that of unfilled UHMWPE. The formation of rigid net (skeleton) formed by CF

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results in a decrease of creep of composite materials under compressive load in

comparison with the unfilled polymer.

5) The tribological tests showed that the friction coefficient of the composites

was more stable as compared with the unfilled UHMWPE. The introduction of carbon

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fibers into UHMWPE raised the wear resistance of the composites. The lowest wear

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was obtained for a composite with 8 wt % of CF: its wear was 2 times lower than that of

unfilled UHMWPE.

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Acknowledgements

The authors gratefully acknowledge the support from RFBR, research project

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No. 14-03-31451 mol_a.
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Fig. 1. (a) UHMWPE powder in the initial state and (b) after ball milling in a planetary

mill for 60 minutes.

Fig.2. X-ray diffraction patterns of the initial UHMWPE powder and UHMWPE

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powder ball-milled for 60 min

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Fig. 3. UHMWPE powder milled for 20 min and then annealed above its melting point

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Fig. 4. The structure of the UHMWPE-CF composite powders after different milling

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times
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Fig. 5 - SEM images of surface after tensile tests (a) and quasibrittle fracture surface (b)

of UHMWPE-based composites reinforced with 8 wt.% of CF

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Fig. 6. UKN-5000 carbon fibers at the initial state

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Fig. 7. The micrographs of UKN-5000 carbon fibers: a, b - after chemical oxidation in

nitric acid for 72 hours; c, d - after thermal oxidation (500 ºC, 10 min.)
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Fig. 8 – The microstructure of composites based on UHMWPE reinforced with

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unmodified (a, b) and modified (after thermal oxidation at 500 °C for 10 minutes) (c, d)
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carbon fibers

Fig. 9 – Young modulus of thermally oxidized at 500 °C for 10 minutes carbon fibers

reinforced UHMWPE based composites

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Fig. 10. (a) Yield strength and (b) Young’s modulus of UHMWPE-based composites

with different CF content at compression tests

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Fig. 11. The time dependences of strain at static load: (a) 5 MPa and (b) 10 MPa

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Fig. 12- Time dependences of (a) friction coefficient and (b) wear under water

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