1 Preparation and Characterization of Composite Materials

2 with Rubber Matrix and Polyvinyl Chloride Additions (PVC)

3 respectively Fly Ash (FA)

4 Dan Dobrota1,*, Cosmin Miritoiu2, Cristinel Sabin Dimulescu1, Ionela Magdalena Rotaru1

15 Faculty of Engineering, Department of Industrial Engineering and Management, Lucian

6 Blaga University of Sibiu, 550024 Sibiu, Romania; dan.dobrota@ulbsibiu.ro (DD);
7 cristi.dimulescu@yahoo.com , (CSD) ionela.rotaru@ulbsibiu.ro (IMR),
28 Faculty of Mechanics, Applied Mechanics and Civil Constructions Department, University of
9 Craiova, 107 Calea Bucuresti Str., 200512, Craiova, Romania
10

11 * Correspondence: dan.dobrota@ulbsibiu.ro

12 Abstract: The analysis of the possibilities of using rubber waste (reclaimed rubber, powder
13 rubber), polyvinyl chloride and fly ash for the obtained of composite materials with high
14 performance was the main objective of the researches. Thus, composite materials were made
15 and tested in which the proportion of waste gradually increased from 50 phr to 150 phr.
16 Composite materials were tested from the point of view of the homogeneity of the structure,
17 but also from the point of view of the physical-mechanical properties. Thus, an SEM
18 analysis, but also a TGA (DTGA) analysis were performed. Also, the behaviour of the
19 composite materials during artificial aging was determined, and at the same time, an analysis
20 of the topography of the surface layer for the tested samples was carried out. From the
21 conducted research it was possible to observe the fact that composite materials with a very
22 good structure homogeneity can be obtained and at the same time a topography of the
23 superficial layer that can be improved by optimizing the composition of such composite
24 materials. Also, the presence of a coupling agent of the KWQ-EL type determines obtaining a
25 good homogeneity of the materials. It was noted that the addition at the same time in the
26 structure of composite materials of both PVC and FA causes a change in the kinetics of the
27 processes that take place during the TGA (DTGA) analysis. At the same time, the
28 optimization of the proportion of FA and PVC determines an improvement of the topography
29 of the superficial layer. Under these conditions, research has demonstrated the fact that
30 sustainable composite materials (economically, socially and environmentally) can be made
31 that can have very good usage properties.

32 Keywords: Rubber, Polyvinyl Chloride, Fly ash, Composite, properties

33 1. Introduction
34 The obtained of high-performance composite materials obtained from recycled materials
35 such as PVC or FA rubber is an important objective of current research, and these can
36 contribute to ensuring a sustainable development considering the 3 components (economic,
37 social, environmental). Currently, it is obvious that there are large amounts of rubber, PVC
38 and FA waste that are not used, generating serious environmental pollution problems. Thus,
39 the incorporation of these wastes into new products with high performance creates conditions
40 for their superior valorization, moving from the recycling phase to the regeneration phase [1-
41 3].
42 Although the problem of reducing the quantities of rubber and PVC waste has been
43 raised lately, the best options for replacing such materials or a superior recovery of the waste
44 from them have not yet been found [4,5]. Also, although recently the problem of replacing
45 coal -fired power plants has been increasingly raised, however, due to the current energy
46 crisis, an extension of the period of use of such energy sources is required [5,6] . This further
47 results in the generation of large amounts of FA that must be further utilized. Better
48 utilization of PVC and FA waste than rubber waste represented and continues to represent a
49 problem that must be treated with particular responsibility in order to manage to considerably
50 reduce environmental pollution [7-9]. Thus, at present, the obtained of composite materials
51 with a rubber matrix with PVC and FA additions can be a sustainable long-term solution.
52 Currently, composite materials with a rubber matrix with different types of additions have
53 been made, but they did not offer the best properties for use. For example, composite
54 materials with rubber matrix and PVC addition have been made that have very good acoustic
55 properties for frequencies above 2500 Hz [10-13]. At the same time, the obtained of rubber
56 mixtures with additions of regenerated rubber from waste allowed to obtain products whose
57 mechanical properties deteriorate very little after the aging process [14-18].
58 Currently, a series of composites based on epoxidized natural rubber have been made
59 (ENR) respectively dimethylformamide (DMF) in which PVC was added, and the results
60 obtained demonstrated that the mixture of PVC with ENR is thermodynamically
61 incompatible. This thermodynamic compatibility resulted from the fact that the addition of
62 PVC in ENR causes the transition temperature in the glass phase (Tg) to change to lower
63 values. It was also found that the mixture of PVC with ENR is thermodynamically
64 incompatible [19-22].
65 Currently, investigations have been made regarding the use of functionalized
66 acrylonitrile-butadiene rubber (NBR-g-MAH) as an impact modifier and compatibilizer in the
67 recycled mixture of PVC and polymethyl methacrylate (PMMA). Thus, it was found that the
68 performance of NBR as an impact modifier was improved by adding maleic anhydride. Also,
69 changing the NBR-g-MAH/NBR blend concentration has different effects on the mechanical,
70 thermal and morphological properties of the recycled blend. Thus, the recycled mixture that
71 has 9% by weight mixture of NBR-g-MAH/ NBR has the best impact resistance and
72 elongation at break. Following the DTA and microscopic analysis, a partial miscibility was
73 observed, as well as the compatibility of the polymer constituents in the mixture. [23-26].
74 Also, current research has demonstrated that the addition of PVC in the structure of
75 various fiber-reinforced rubber composites can cause an increase in tensile strength,
76 elongation at break and greater impact resistance, but also an improvement in adhesion at the
77 interface between matrix and fibers [27, 28 ] . A possible variant of the composite that has
78 been welded recently is that made of the PVC/NBR ( nitrile butadiene rubber)/nanoclay type,
79 and in its case it was demonstrated that the fracture surface of the specimens was much
80 smoother, compared to the situation in which only NBR is used. Starting from these
81 researches, other current researches have analyzed the PVC/NBR composites in which
82 graphene nanoplates (GNP) and organoclay montmorillonite (OMMT) were added on the
83 strengthening, relaxation and mechanical properties of the nanocomposites (NBR/PVC).
84 Thus it was found that the addition of both GNP and OMMT causes an improvement in the
85 tensile strength of the modulus of elasticity and hardness [29,30].
86 Also, composites were made from mixtures of PMMA (Polymethyl methacrylate), PVC
87 and NBR respectively, and an improvement in impact performance and elongation at break of
88 the recycled mixture was obtained compared to NBR. At the same time, composites based on
89 low density polyethylene (PE) with different natural rubber (NR) content (10-30% by weight)
90 were made. Such composites had an increased biodegradability, and this allows their
91 successful use for making biodegradable packaging [31, 33]. As for FA, it can be used as a
92 filler to make rubber products with less good usage properties. Thus, there is the problem of
93 finding technical solutions to incorporate increasing amounts of FA in rubber products, but
94 with maintaining the best possible properties of their use. All this demonstrates the fact that it
95 is necessary to identify the best technical solutions for the efficient use of FA because an
96 inadequate disposal of FA causes serious environmental problems in the surrounding areas by
97 contaminating the air, soil and groundwater [34,35].
98 Currently, various technologies have been tried to use FA in the composition of various
99 elastomers, but these technologies could not be developed properly due to the fact that there
100 is a low capacity to incorporate FA in rubber matrix products [36]. A number of current
101 researches have demonstrated that in order to achieve a good incorporation of FA in rubber
102 matrix composites it is possible by using different types of coupling agents [37,38]. In this
103 sense, the use of silane-type coupling agents is recommended because they can add additional
104 crosslinking to the rubber [39]. Current research [40,41] has considered the incorporation of
105 small amounts of FA (up to 20 phr), and up to these levels of FA it has been shown that the
106 effect of FA is approximately the same as that determined by the addition of silica in rubber
107 compounds. Considering the high cost of silica in relation to FA, it follows that its use allows
108 obtaining much cheaper rubber products [42-44]. Also, in addition to reduced costs, a good
109 machinability of rubber products can be obtained due to the fact that the shape of the FA
110 particles is predominantly spherical. The use of FA in various rubber products can increase
111 the elongation at break of composite materials by 35%, and the abrasion resistance by 64%
112 [45,46].
113 From the analysis of the specialized literature, it was found that over time several
114 researches were developed with the aim of reusing some waste materials (rubber, FA, PVC).
115 All the researches have generally used separately PVC and FA respectively in the structure of
116 composites with rubber matrix. Thus, the main objective of the research was the obtained of
117 composite materials with high usage properties that have in their composition both materials
118 made from rubber waste and PVC respectively FA. The work was structured, according to the
119 objective of the research, in a section where the properties of the materials used were
120 analyzed, respectively technological aspects related to obtaining composite materials. In the
121 results and discussion section, the main characteristics of the analyzed composite materials
122 were presented. Thus, these materials were subjected to SEM, TGA (DTGA) analyses,
123 artificial aging, respectively the determination of the topography of the superficial layer.
124 2. Materials and methods

125 2.1. Materials

126 2.1.1. Composition of composite materials

127 To carry out the experiments, 5 types of composite materials were made starting from a
128 rubber mixture (S01) that had in its composition both reclaimed rubber and rubber powder
129 obtained from tire waste recycling. Starting from this rubber mixture, new composite
130 materials were made by adding PVC (S02), FA (S03), PVC and FA in moderate amounts
131 (S03) and PVC respectively FA in very large amounts (S05), Table 1.
132 Additionally, vulcanizing solutions GDT + 5% Desmodur R type crosslinking agent
133 produced by Covestro AG (Leverkusen, Germany) and trichlorethylene for pickling
134 operations were used. The determination of the composition of the 5 types of samples was
135 made considering the main objective of the research, namely the analysis of the possibility of
136 obtaining the best performing composite material using material resulting from waste
137 recycling. Thus, if in the case of sample S01 a proportion of 50 phr (reclaimed rubber +
138 rubber powder) is represented by material resulting from waste recycling, in the case of
139 sample S05 the proportion has increased to 150 phr (reclaimed rubber + rubber powder +
140 PVC+FA ).
141 Table 1. The composition of composite materials
Materials The Composite Materials
Compound, phr
 S01 S02 S03 S04 S0
5

Natural rubber (Standard Indonesia Rubber-20) 15 15 15 15 15

Styrene-butadiene synthetic rubber (SBR-1723 TDAE) 20 20 20 20 20

Poly-butadiene synthetic rubber SKD ND (Nizhnekamsk

15 15 15 15 15
Russia)

Reclaimed rubber (ARTEGO Romania) 30 30 30 30 30

Rubber powder with size 80-100 µm (ARTEGO,
20 20 20 20 20
Romania)

Carbon black HAF 330 18 18 18 18 18

Antioxidant 4010NA/LG(IPPD) (HENAN, GO

3 3 3 3 3
BIOTECH, China)

Stearin 5 5 5 5 5

coupling agent KWQ-EL 5 5 5 5 5

Pure talcum powder (Merck KGaA, Darmstadt, Ger-

17 17 17 17 17
many)
Vulcanization accelerator DPG ( standard Q/CNPC55-
4 4 4 4 4
2001)
 Sulphur 3 3 3 3 3

GDT + 5% Desmodur R 5 5 5 5 5

Fly ash (Energetic Complex Oltenia, Romania) 0 30 0 30 50

Polyvinyl Chloride ( Crillelmar SRL, Targu Jiu,
0 0 30 30 50
Romania)
Total 175 205 205 235 275

142 2.1.2. Characterization of FA

143 The FA used in the experimental research was obtained from the combustion of lignite in
144 the power plants of Energetic Complex Oltenia, Romania. Because FA with various
145 properties can result during the combustion of lignite, 10 samples were taken and analyzed
146 from the point of view of grain size, chemical composition and SEM images. Also, the FA
147 subjected to the analyzes was initially subjected to a grinding process for an improvement of
148 the granulation.

∑ N i ∙ Di
D n= i (1)
∑ Ni
i

∑ N i ∙ Di4
i
Dw= (2)
∑ N i D3i
i
 Dw
PDI= (3)
Dn

149 The ground FA was initially analyzed from the point of view of polydispersity by optical
150 microscopy, and the obtained values were processed by analysis of variance (ANOVA).
151 Thus, the estimation of the average size of FA particles (average numerical size Dn, average
152 gravimetric size Dw) and polydispersity index (Dw/Dn) was achieved by measuring 100
153 particles.
154 where : Ni represents the number of particles that have the size Di.
155 After measuring the particle sizes and calculating the average numerical size Dn,
156 respectively the average gravimetric size Dw, the value of the polydispersity index PDI =
157 0.911 was determined, which indicates a homogeneous dispersion of the particle sizes.
158 To establish the granulometric distribution of the particles, Figure 1, their sizes were
159 measured using laser diffraction using a Laser Diffraction Microtrac MRB manufactured by
160 215 Keystone Dr, Montgomeryville, PA 18936, USA. It was observed that FA had a
161 distribution, generally, in the 2-8μm range. Most of the particles have a diameter of about
162 5μm.
163
164
165 Figure 1. Grain size distribution of fly ash measured by laser diffraction.
166

167 In order to establish the phase composition, the X-ray analysis of FA was used, which
168 was carried out with the X-ray diffractometer DE X'Pert PRO MPD, PANALYTICAL. Phase
169 composition for FA shows that in the phase composition, there are three crystalline
170 components: quartz, mullite and hematite, Figure 2.
171
172 Figure 2. X-ray diffraction patterns of the FA.
173

174 Also, to establish the properties of FA more clearly, a chemical composition analysis was
175 also carried out, and the results, methods and equipment used are shown in Table 2.
Chemical composting Content (% by weight) Methods Equipment
Silica (SiO 2 ) 53.17 X-ray analytical
Aluminum oxide (Al 2 O 3 ) 19.03 microscope – XGT
Ferric oxide (Fe 2 O 3 ) 1.33 9000 - The
Calcium oxide (CaO) 4.05 fluorescent X-ray
X-ray
Magnesium oxide (MgO) 4.71 detector can detect
fluorescence
Potassium oxide (K 2 O) 4.96 from Americium
 (XRF) down to carbon, with
Sodium oxide (Na 2 O) 3.76 a light elements
Titanium dioxide (TiO 2 ) 3.41 detector – produced
Sulfur trioxide (SO 3 ) 1.92 Horiba, Kyoto 601-
Loss on Ignition - LOI 3.66 8510 Japan

176 Table 2. Chemical composition of FA respectively methods and equipment used.

177

178 A high-resolution scanning electron microscope ( Phenom PURE, Thermo Fisher

179 Scientific, Netherlands ) was used for the SEM analysis of the FA samples, and the resulting
180 image is shown in Figure 3.
181 Figure 3. SEM image for FA.

182 2.1.3. Characterization of PVC particles

183 The PVC particles were supplied to Crillelmar SRL, Targu Jiu, Romania, and these
184 particles were obtained from waste recycling, Figure 4.
185 Figure 4. PVC particles
186

187 The physical-mechanical properties of the PVC particles, according to the specifications
188 given by the manufacturer, are presented in Table 3.
189 Table 3. Properties of PVC particles
Properties
Thermal con- Yield Resistiv- Surface res-
PVC Density ,
ductivity strength ity istivity
particle g/cm 3
W/(m K ) MPa Ω ·m Ω
1.1÷1.35 0.14÷0.17 10÷24.8 10 12 –10 15 10 –10 12
11

190

191 The size of the particles and its distribution is an important property of PVC that can
192 influence the final properties of the composite material. Regarding the PVC particles, they
193 were also characterized from the point of view of polydispersity according to those presented
194 in the case of FA. Thus, it was established that the size of the PVC particles used had values
195 in the range of 1.5 ÷ 2 mm. After measuring the dimensions of the particle and calculating the
196 numerical average size D n , respectively the gravimetric mean size D w , the value of the
197 polydispersity index PDI = 0.893 was determined.

198 2.2. Methods of obtaining and testing specimens

199 2.2.1. The technology of obtaining samples

200 Obtaining composite materials with rubber matrices involves several technological
201 operations, but a first operation consists in the homogenization of the materials used. This
202 homogenization operation was applied to all the samples obtained, even in the case of the
203 sample without FA/PVC additions, so that all the components that enter the structure of the
204 materials are as well distributed as possible. In the case of FA, it was first homogenized and
205 mixed with the used coupling agent KWQ-EL, produced by ARTEGO, Târgu Jiu, Romania
206 using a mixer for 2.5 minutes. All the materials used for the 5 types of specimens were mixed
207 in a cylinder-type equipment that had a temperature of 50 ℃ and a rotation speed of 25
208 r/min.
209 After the homogenization of the materials for the 5 types of samples, the next operation was
210 carried out, which consisted of a vulcanization process using a hot vulcanization press of the
211 DSLQ type, produced by Wagener Schwelm Corporation (Reisholzstraße, Hilden, Germany.
212 The choice of this type of the press to be vulcanized was realized because it allows the
213 adjustment of the vulcanization parameters (pressure, temperature) in a very wide range. The
214 adjustment of the vulcanization parameters was made so that there is a correlation of pressure
215 with vulcanization temperature as follows:
216  temperature 25°C - 45°C - pressure 70 bar;
217  temperature 45°C - 75°C - pressure 85 bar;
218  temperature 75°C-105°C - pressure 110 bar;
219  temperature 105°C-120°C - pressure 125 bar;
220  temperature 120°C-145°C - pressure 160 bar;
221 As for the heating time for vulcanization, it was calculated from the moment of reaching
222 a temperature of the heating plates of the vulcanizing press of 100°C. Regarding the duration
223 of vulcanization of the samples, this was 50 min. After the expiration of the 50 min duration,
224 the heating process was stopped, and the cooling was done slowly keeping the pressure of
225 160 bar until the temperature reached the value of 60°C. It was necessary to cool the samples
226 after vulcanization under pressure to avoid the formation of pores in the structure of the
227 materials.

228 2.2.2. Establishing the structure of the material in the samples

229 A very important factor that can influence the properties of polymer matrix composite
230 materials is their microscopic structure. Thus, the microscopic structure of composite
231 materials can decisively influence their physical-mechanical properties. Also, through
232 microscopic analysis, certain inhomogeneities, microcracks or voids that may appear inside
233 the composite materials can be highlighted. In this sense, scanning electron microscopy
234 (SEM) of the Thermo Scientific Phenom XL G2 type, produced by Thermo Fisher Scientific,
235 Netherlands, was used for the analysis. This type of equipment, due to its characteristics,
236 offers the possibility of obtaining the best results in the analysis of the structure of composite
237 materials.
238

239

240 2.2.3. Thermogravimetric analysis (TGA) of composite materials

241 Thermogravimetric analysis provides the possibility of quantitative measurement of the

242 change in mass of materials. TGA records the change in mass from dehydration,
243 decomposition, and oxidation of a sample as a function of time and temperature. Similarly,
244 thermogravimetric analysis measures the percent weight loss of a test sample while the
245 sample is heated at a uniform rate in a suitable environment. Weight loss over certain
246 temperature ranges gives an indication of sample composition, including volatiles and inert
247 filler, as well as indications of thermal stability. A TGA Q 50 thermogravimeter provided by
248 TA Instruments Headquarters: 159 Lukens Drive, New Castle, DE 19720, USA was used in
249 the experimental research. Following the TGA analysis, 2 curves were drawn showing the
250 weight (%) as a function of the temperature (°C) drift. weight (%/°C) as a function of
251 temperature.
252 Samples were loaded (placed) on platinum crucibles, their maximum admissible mass
253 must not exceed 1g. The TGA analysis was carried out using the ramp rate, with the
254 maximum heating temperature of 500°C, the heating speed 10°C/min, the samples were
255 analyzed with the equipment software, TGA Universal Analysis 2000, the test was done in a
256 nitrogen environment, with purity 5.0. The maximum heating temperature of 500 0
C was
257 chosen because after this temperature the weight loss of the rubber composites stabilizes. The
258 working environment was made by means of a nitrogen cylinder connected to the apparatus,
259 and for all experiments it was used:
260 - Xcomment Pan: Platinum;
261 - Xcomment Gas1: Nitrogen;
262 - Xcomment Gas2: Nitrogen;
263 - Xcomment Balance Gas: Nitrogen 40.0 ml/min;
264 - Xcomment Sample Gas: Nitrogen 60.0 ml/min;
265 - AirCoolTime 10.0 min.

266 2.2.4. Testing of rubber specimens from the point of view of thermal shock behaviour.

267 A very important property of all materials, but especially of rubber matrix composites,
268 refers to their behaviour during aging processes. We analyzed this property because rubber
269 matrix composite materials are used to make parts that are subjected to different temperature
270 variations during use. In order to observe how these composite materials behave under
271 various thermal shocks, they were subjected to an artificial aging process. Thus, the elastic
272 properties of the samples were determined after the technological process of obtaining but
273 also after the application of thermal shocks.
274 The testing of the behaviour of the composite materials from the 5 types of specimens
275 was carried out using a thermal chamber, Temp Shock test chamber Votsch VT3 7012 S2
276 produced by Test Equipment Co., Ltd Jin Hui Industrial Park, China. This type of thermal
277 chamber allows very fast temperature changes in the range of -80°C - 220°C. Because in
278 practical conditions products from these types of composite materials are used in
279 environments with temperatures ranging from –45°C to +85°C and the test conditions were
280 the same. Thus, the samples were tested for 3000 cycles with temperature variations in the
281 range of –45°C to +85°C. The settling times also varied and thus a time of 60 minutes was set
282 for the first 1000 duty cycles and 25 minutes for the next 2000 duty cycles. The
283 accommodation was made under the conditions of an environment subject to the ventilation
284 process.
285 The elastic properties of the composite materials were determined using a Zwick/Roell
286 Z05 TN apparatus with testXpertII version 3.6 software produced by BRECON
287 Vibrationstechnik GmbH Stolberger, Köln , Germany. The choice of this type of device was
288 made considering the fact that it presents a multitude of options and thus by using zwickiLine
289 properties can be determined for plastic materials, elastomers, metals, composites, paper,
290 cardboard, textiles, foams and food products respectively. Regarding the penetrator used in
291 the testing process, the former one with a spherical head with a diameter of 7.96mm and a tip
292 radius of 3.98mm.

293 2.2.5. Testing the samples from the point of view of the topography of the superficial
294 layer
295 The surface topography for the analyzed composites was determined using a scanning
296 electron microscope (SEM) ( Phenom PURE, Thermo Fisher Scientific, Netherlands ). The
297 analysis of the topography of the surfaces of composite materials is very important because in
298 the conditions in which an appropriate microgeometry cannot be obtained, certain adhesions
299 with certain impurities may appear on the surfaces of the materials, as well as the location of
300 some water vapors. Thus, the microgeometry of the surface layer produces effects on how
301 certain impurities or water vapour can adhere to the surfaces of the materials. Thus, the
302 obtained of composite materials with a very low roughness of the surface layer prevents the
303 formation of adhesions and this has good effects on improving the resistance to abrasive wear
304 of the products.

305

306

307

308 3. Results and Discussion

309 3.1 Analysis of the microscopic structure of composite materials

310 SEM analysis was used to study the internal structure of the composite materials. Thus,
311 through SEM analysis, the morphology of the particles in the composite materials was
312 studied, as well as the distribution of fillers and additives to identify any defects or impurities
313 present in them. Also, through SEM analysis, the interface between the rubber matrix and the
314 ash and PVC additions was studied, which is very important because it affects the physical-
315 mechanical properties of the composite material. The surface morphology of composite
316 materials can be used to study the damage mechanisms of composite materials, but also to
317 determine their suitability for making various products. Under these conditions, in the first
318 stage of the research, an SEM analysis of the material structure of the 5 samples was carried
319 out.
320 The SEM images of the material from the 5 samples (S01-Figure 5.a, S02-Figure 5.b,
321 S03-Figure 5.c, S04-Figure 5.d, S05-Figure 5.e) present information on the affinity between
322 the materials used and their dispersion in the structure of the composites. Also , the SEM
323 analysis can highlight a tendency for the formation of certain pores in the structure of the
324 composites. Figure 5.a shows an SEM image of the sample made of rubber mixtures, but in
325 which reclaimed rubber and powder rubber are also found. Thus, from the SEM analysis it
326 can be observed that there is a very good compactness of the material, but there are also
327 certain whitish areas determined by the fact that in the process of obtaining reclaimed rubber
328 talcum powder is also used, respectively by the presence of certain impurities present in
329 powder rubber . After the addition of FA, the material corresponding to sample S01 was
330 obtained, which has a composition of 30 phr, and the SEM analysis for this material is
331 presented in Figure 5.b. From the SEM analysis, it was observed that there was a strong
332 interaction between FA rubber, which is determined by the fact that there is a large amount of
333 SiO2 in the FA composition, and the silica particles form strong filler-filler interactions with
334 the adjacent silica particles [47 , 48]. Also, the presence of certain amounts of sulfur in the
335 FA structure can add additional crosslinking to the polymer [49]. At the same time the use of
336 KWQ-EL can improve the compatibility between the FA and the rubber matrix. The
337 compactness of the material obtained in the case of sample S02 was very good with very
338 small porosities comparable in size to those obtained in the case of sample S01. A substantial
339 difference was observed in the case of sample S01 refers to the color of the matrix which is
340 lighter compared to sample S01 and this is explained by the fact that FA was added. The
341 SEM analysis of the S02 sample containing FA demonstrated the fact that it is possible to
342 obtain rubber products in which FA is added with very good structural homogeneity.

(a)
(b)

(c)
 (d)

(e)
343

344 Figure 5. SEM images for the composite materials from the 5 types of samples: a – sample
345 S01; b – sample S02; c – sample S03; d – sample S04; e – sample S05.
346
347 After the addition of PVC in the rubber composition, the S03 sample was obtained, and
348 from the SEM analysis it was observed that the addition of PVC causes an increase in the
349 porosity of the material. This was also observed in the case of SEM analyzes for samples S04
350 (Figure 5.d) and S05 (Figure 5.e). It is worth noting that the highest porosity was obtained in
351 the case of sample S05 which contains a large amount of both Fa and PVC. A possible
352 solution to eliminate the pores that appear in the case of the addition of PVC would be the use
353 of ultrasound in the vulcanization process whose presence causes a uniformization of the
354 temperature and pressure inside the material during the vulcanization process [50,51]. Also,
355 this PVC/rubber matrix compatibility can substantially influence the elastic properties of both
356 new and aged materials. In order to observe the elastic properties of composite materials, an
357 analysis of their behavior during an artificial aging process was carried out in section 3.3.
358

359

360 3.2. Get results from the analysis thermogravimetric (TGA) of composite materials

361 The TGA–DTGA results, using the high-resolution TGA approach, obtained from the 5
362 types of composite material (S01, S02, S03, S04, S05) are shown in Figure 6. This analysis
363 method allows, in a shorter experimental time and with high resolution weight loss analysis
364 of composite materials at different temperatures. The TGA curve will usually indicate the
365 decomposition of composite materials into their constituent components, such as carbon
366 black and filler, etc. as the temperature increases. TGA can also be used to determine the
367 thermal stability of the composite material, the onset and peak temperatures of degradation,
368 and the total weight loss of the material. TGA analysis for PVC is used to study the thermal
369 stability of PVC compounds with various additives such as plasticizers and stabilizers. At the
370 same time, TGA also indicates the weight changes of FA as a function of temperature, and
371 the TGA curve for fly ash usually shows a gradual weight loss as the temperature increases,
372 which is due to the thermal degradation of the organic compounds present in fly ash [52,53].
373 The TGA curve also helps to identify the temperatures at which specific compounds in fly
374 ash begin to degrade [54]. In the case of all 5 composite materials, weight loss occurs even at
375 very low temperatures, and this weight loss is attributed to the volatilization of processing oil
376 or any other low-boiling components. Regarding the S01 composite material that does not
377 have FA or PVC in its composition, it was observed that the total weight loss at 500 oC was
378 approximately 50%, and this corresponds to the rather large presence in the composition of
379 inorganic filler components but also a rubber powder. Since DTGA curves can be used to
380 identify and quantify the ratio of elastomers in mixtures, the correlation of peak heights with
381 the content of each component, they provided information related to the speed of weight loss
382 at different temperatures From the analysis of the DTGA curve, Figure 1.a, it was observed
383 that there a high weight loss rate of 270.74oC, and this is due to the decomposition of natural
384 rubber (NR), while the high rate of C loss with a DTGA peak at 466.1 oC corresponds to the
385 decomposition of styrene-butadiene rubber (SBR) respectively poly-butadiene synthetic
386 rubber (SKD ND) . It is worth noting that at the temperature of 362.11 oC it was observed that
387 there is an area of decrease in the rate of weight loss, and this may be due to the fact that the
388 decomposition process of NR was finished, and the other components of the composite
389 material did not they.
390 Regarding the composite material containing FA, following the TGA analysis, it was
391 observed that the total weight loss was approximately 55% higher by 5% compared to the
392 situation analyzed in the case of the composite material that did not contain FA. Also, the
393 maximum rate of weight loss was observed at a temperature of 281.03 o C, which is above the
394 temperature of sample S01, but also at a temperature of 461.74 o C, which is slightly lower
395 than in the case of sample S01. Thus, it was demonstrated that the addition of FA in the
396 composite material with rubber matrix does not substantially change either the total weight
397 loss or the temperatures at which the weight loss occurs at the highest speed. This can be
398 explained by the fact that due to the fact that the analyzed FA contains very fine fractions of
399 ash or compound minerals (mainly silica) and in this way a very good reaction with silanes
400 (KWQ-L) is produced. Also, the decrease in temperature from 466.1 o
C to 461.74 o C at
401 which the second stage of high-speed weight loss occurred can be explained by the presence
402 of a certain fraction of FA with larger grains that are not able to react chemically with silanes
403 and thus the temperature at which weight loss occurs changes.
404 In the case of composite materials (S03) in which PVC is added in a moderate
405 proportion, a total weight loss of approximately 50% was observed, so approximately the
406 same as in the case where PVC is not present in the composite material (S01). It is worth
407 noting that in the case of S03, the temperatures at which weight loss occurs at the highest rate
408 change. It is noteworthy that a first stage of high rate weight loss starts at a temperature of
409 about 185°C (T0) and ends at 335°C. The second high-speed degradation stage starts at about
410 335 °C (T02) and ends at 462.19 °C. The thermal degradation in this last step is due to the
411 fact that they can appear in the structure of the composite material of the polyene sequences
412 that produce volatile aromatic and aliphatic compounds through the intramolecular
413 cyclization of the conjugated sequences.
414 After the analysis of the composite materials S01, S02, S03, the next step was the TGA
415 analysis of the composites containing both FA and PVC at the same time. Thus, S04 contains
416 FA (30phr) and PVC (30phr), and in the case of the S05 composite material, the proportion of
417 FA and PVC increased considerably, reaching 50phr. It is worth noting that in the case of
418 both composite materials (S04, S05) the total weight loss is greater than 55% with some
419 increase in the case of sample S05 which contains larger amounts of FA and PVC
420 respectively. Also, from the DTGA analysis it was observed that there are two temperature
421 ranges in which mass loss occurs at a very high speed, namely the first temperature range
422 (245 o
C – 285 o
C) and the second temperature range in which a very fast weight loss
423 occurred (415 o C – 460 o C). These results can be explained by the thermal decomposition of
424 polyaniline that is formed during the process of obtaining composite materials that have both
425 FA and PVC in their structure. At the same time, it was also confirmed that the presence of
426 the KWQ-EL coupling agent can have a certain affinity towards PVC, and this can cause an
427 increase in the loss rate, especially in the temperature range 245 o C – 285 o C [55,56]. It is
428 also worth noting that with the increase in the amount of FA and PVC, the total weight loss
429 decreases from 58% to 55%. Thus, from the analysis of the TGA/DTGA curves, it can be
430 confirmed that the thermal stability of the S04 and S05 composites decreases compared to the
431 S01 sample, which does not have FA or PVC in its composition. All these results may be due
432 to the interaction between FA and PVC. Also, this interaction can be explained by some lack
433 of connection between the filler materials and the rubber matrix, something also observed
434 from the SEM analysis presented in Figure 5.d and Figure 5.e.
435

(a)
(b)
(b)
(d)
 (e)
436 Figure 6. TGA analysis for the composite materials from the 5 types of samples: a – sample
437 S01; b – sample S02; c – sample S03; d – sample S04; e – sample S05;
438 3.3 . Thermal shock behavior of rubber matrix composite materials.
439 Since most of the products made of composite materials with rubber matrix are subjected
440 during use to an aging process, the behavior of the 5 types of composite materials to this type
441 of request was followed in the research. Also, the analysis of the behavior of composite
442 materials to thermal shocks is useful to be able to determine the useful life of the products
443 and to optimize the composition of these types of materials. Thus, the 5 types of materials
444 were subjected to an artificial aging process that allows simulating the effects of long-term
445 exposure to different temperature variations. The research involved the exposure of
446 composite materials to temperature variations in the range of –45°C to +85°C . Artificial
447 aging can produce changes in the physical and mechanical properties of composite materials,
448 and thus changes in elasticity were analyzed in the research. The obtained results can be used
449 to improve the performance and durability of rubber matrix composite products. Thus, the 5
450 types of composite materials were subjected to an accelerated aging process. Accelerated
451 aging of the tested composite materials was carried out according to the S R ISO 188:2010
452 standard. In these it was determined how the elasticity of materials is modified by measuring displacement
453 for certain applied forces. The testing was carried out considering both the material from the
454 new specimens and the one subjected to the accelerated aging process. The testing was
455 carried out considering a pressing speed of the penetrator of 30 mm/min and several stages
456 involving different pressing forces were considered: stage 1 – F = 10 N; stage 2 – F = 50 N;
457 stage 3 – F = 75 N; stage 4 – F = 100 N; stage 5 – F = 150 N; stage 6 – F = 200 N; stage 7 – F
458 = 400 N. The results obtained after testing the elasticity of the material in the samples are
459 presented in Figure 7.a – the initial S01 material; Figure 7.b – S01 material after aging;
460 Figure 7.c – initial S02 material; Figure 7.d – S02 material after aging; Figure 7.e – initial
461 S03 material; Figure 7.f – S03 material after aging; Figure 7.g – initial S04 material; Figure
462 7.h – S04 material after aging, Figure 7.i – initial S05 material; Figure 7.j – S05 material after
463 aging. .
464 From the analysis of the results presented in Figure 7, it can be observed that an artificial
465 aging process causes a loss of elasticity of the materials, but this loss is smaller or larger. In
466 practice it would be very good for a material to have very little loss of elasticity following the
467 application of aging. As for the material in sample S01, it did not have a very high elasticity
468 due to the presence in the composition of reclaimed rubber and powder rubber respectively,
469 Figure 7a and Figure 7.b, respectively. It is also noteworthy that this composite material had a
470 fairly low loss of elasticity of only about 10%. The addition of FA in the composition of the
471 materials, SO2, caused an increase in initial elasticity of about 12%, but also a very low loss
472 of elasticity of 8%. This result confirms that the addition of FA allows both an increase in the
473 elasticity of the initial material, but also a fairly good elasticity stability following the aging
474 process.
475 The addition of PVC in the structure of the composites determined an increase in
476 porosity according to the SEM images, but also a decrease in the initial elasticity of the
477 composites due to the low elasticity properties that PVC has (Figure 7.e respectively Figure
478 7.f). It is worth noting that the elastic modulus is also very small for this type of composite
479 material. Under these conditions, it can be concluded that composite materials that have a
480 PVC composition can be successfully used to make products that do not have to have a high
481 elasticity, but which must have a very good aging behavior. The realization of composite
482 materials by adding both FA and PVC (S04, S05) was carried out in order to be able to find
483 an optimal composition of composite materials that have both high elasticity and a very good
484 behavior in the aging process.
485 The addition of large amounts of FA and PVC respectively in the presence of the KWQ-
486 EL coupling agent causes the appearance of a large amount of rubber rubber/FA/silica/PVC
487 compounds that have a very good behavior when aging [57, 58]. This behavior can be
488 attributed to the distinct characteristics of the filler materials and the types of bonds that are
489 created between the different materials introduced into the composites. The existence of
490 ineractions between the materials in the composite can both contribute to the improvement of
491 the elastic properties, but at the same time it can contribute to a substantial increase in the
492 aging resistance [59]. Thus, greatly increasing the amount of PVC respectively FA (S05)
493 allows both an increase in the elasticity of the composite materials under the conditions of a
494 moderate loss of elasticity following the aging process (Figures 7.i and Figure 7.j
495 respectively). Under these conditions, the conducted researches bring an important scientific
496 contribution in the field, demonstrating the sustainability of composite materials with rubber
497 matrices and additions of FA and PVC respectively.
 450 450
400 400
350 350
300 300
Force [N]

Force [N]
250 250
200 200
150 150
100 100
50 50
0 0
0 0.5 1 1.5 2 2.5 3 3.5 0 0.5 1 1.5 2 2.5 3
Displacement [mm]
Displacement [mm]

(a) (b)
450 450
400 400
350 350
300 300
Force [N]

250
Force [N]

250
200 200
150 150
100 100
50 50
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 0 0.5 1 1.5 2 2.5 3 3.5
Displacement [mm] Displacemnet [mm]

(c) (d)
 450 450
400 400
350 350
300 300

Force [N]
Force [N]

250 250
200 200
150 150
100 100
50 50
0 0
0 0.5 1 1.5 2 2.5 3 0 0.5 1 1.5 2 2.5
Displacement [mm]
Displacement [mm]

(e) (f)

450 450
400 400
350 350
300 300
Force [N]
Force [N]

250 250
200 200
150 150
100 100
50 50
0 0
0 1 2 3 4 5 6 0 0.5 1 1.5 2 2.5 3 3.5 4
Displacement [mm] Displacement [mm]

(g) (h)
 (i) (j)
498 Figure 7. Standard displacement obtained for different forces applied to the composite
499 materials from the 5 types of samples: a – the initial S01 material; b – material S01 after
500 aging; c – initial S02 material; d – S02 material after aging; e – initial S03 material; f – S03
501 material after aging; g – initial S04 material; h – S04 material after aging, i – initial S05
502 material; j – S05 material after aging.
503 3.4. Results obtained from the analysis of the topography of the superficial layer of the
504 samples
505 The topography of the surface layer of composite materials mainly refers to the surface
506 characteristics of the material. This can include the roughness, texture and general shape of
507 the surface. The topography of the surface layer can have a significant impact on the overall
508 performance and properties of the composite material, such as strength, durability and wear
509 resistance. It can also affect the aesthetic appearance of the material and its ability to interact
510 with other materials or components. The topography of the surface layer can often be
511 controlled by the manufacturing process, such as by the use of specialized tools or techniques
512 to shape and finish the surface of the composite material, but also by the composition of the
513 composite material.
514 The research carried out mainly focused on the influence that the composition of the
515 composite material has on the topography of the surface layer. Thus, the topography of the
516 sample S01, which has only rubber in its structure (Figure 8.a), as well as the composite
517 materials formed from mixtures of rubber and FA (Figure 8.b), mixtures of rubber and PVC
518 (Figure 8.c) was analyzed , but also FA and PVC rubber mixtures (Figures 8.d and 8.e).
519 Under these conditions, it was possible to determine the influence of the use of FA and PVC
520 on the surface roughness of the composite materials. The high roughness of the layer can
521 influence how certain substances can adhere to the surfaces of the composite materials made.
522 Some researches [60-61] also specify that a high roughness of the surface layer can
523 significantly influence the aging processes of composite materials with rubber matrix because
524 a high roughness can accelerate the aging process by forming a network of microcracks in the
525 surface layer .
526 The analysis of the topography of the surface layer of the samples was carried out in 4
527 directions and the result is an average roughness of the surface. From the analysis of the
528 average surface roughness of the samples, it was observed that the lowest roughness was
529 obtained in the case of sample S01 (Sa = 1.41µm) which has in its composition different
530 types of rubber but also reclaimed rubber and powder rubber respectively. Also, by adding
531 FA or PVC to the composite materials, it changes the roughness of the superficial layer in the
532 sense of increasing it. The largest increase in surface layer roughness was observed in the
533 case of composites with rubber matrix and PVC addition when the roughness increased by
534 about 50% reaching Sa = 2.16 µm. This increase in roughness can be explained by the
535 different bonds that are made between rubber and PVC, but also by the relatively high grain
536 size of PVC. Figure 8. SEM images for the composite materials from the 5 types of samples:
537 a – sample S01; a – sample S02; a – sample S03; a – sample S04; a – sample S05.
538

(a)
(b)
(c)
(d)
 (e)
539 Figure 8. SEM images for the composite materials from the 5 types of samples: a – sample
540 S01; b – sample S02; c – sample S03; d – sample S04; e – sample S05.
541

542 In the case of the samples made only by adding FA, it was found that the roughness of
543 the surface layer increases, but to a much lower extent than when PVC was added. This
544 difference in the surface roughness of the samples with FA and PVC can be explained by the
545 kinetics of vulcanization and processability of the rubber compounds that can be influenced
546 by the presence of the two components. It is worth noting that in the case of the samples
547 containing both FA and PVC, an improvement in the roughness of the surface layer was
548 found. Thus, in the case of the S05 samples containing large amounts of PVC and FA, the
549 roughness of the surface layer was substantially improved, obtaining a roughness Sa =
550 1.71µm which is not much higher compared to the case of samples containing only rubber.
551 Under these conditions, it can be concluded that an optimization of the content of FA or PVC
552 composite materials can determine a reduction of the roughness of the surface layer. This
553 improvement in surface topography following the addition of large amounts of FA and PVC
554 can be explained by the effect that the presence of FA together with PVC has on the increase
555 of rubber-FA-PVC interactions. This phenomenon is in agreement with the previous study
556 that refers to the modification of the specific surface area, surface energy, respectively the
557 dispersion of the bonds in the rubber matrix [62].
558 Also, an influence on the topography of the superficial layer can be had by the size of the
559 PVC or FA particles, their modality inside the rubber matrix or their molecular architecture
560 [63]. At the same time, the increase in roughness can also be explained by the tendency to
561 form areas with agglomerated particles on the surface of the polymer. By increasing the
562 amount of FA and implicitly the amount of SiO2, a better incorporation of PVC in the
563 structure of the composites can be obtained due to the improvement of the interaction
564 between the particles of SiO2, PVC and rubber [57,58]. The better roughness obtained in the
565 case of the S05 sample containing a large amount of FA can also be explained by the fact that
566 the presence of a large amount of Al2O3 causes a migration of the particles containing SiO2
567 and Al2O3 to the outer surfaces of the composites, creating conditions for improving the
568 roughness in depending on the particle size.
569 Considering the fact that the objective of the research was to obtain composite materials
570 by adding materials from waste (PVC, FA), it was demonstrated that composite materials can
571 be obtained at low costs and with a very good topography of the superficial layer. At the
572 same time, by reusing PVC and FA waste, the amount of hard-to-recyclable waste can be
573 minimized, ensuring their efficient use by incorporating them into new materials.
574

575

576

577

578 4. Conclusions
579 The research carried out with the objective of obtaining composite materials with high
580 properties made from waste rubber, FA and PVC respectively demonstrated the following:
581 - it is possible to obtain composite material from waste that has high performance in
582 operation, provided that their composition is optimized ;
583 - the analysis of the SEM images carried out demonstrated the fact that a higher
584 porosity is obtained for materials that have FA in their composition, but especially in
585 the case that they contain PVC. It was also noted that a fairly good homogeneity of
586 the materials can be obtained if a suitable coupling agent of the KWQ-EL type is
587 used;
588 - TGA/DTGA analysis demonstrated that the addition of FA and PVC causes a
589 change in the weight loss values, but also in the temperature ranges where weight
590 loss occurs. However, these weight losses are not very high and thus this type of
591 composite materials can be used in multiple industrial applications;
592 - the use of large quantities of PVC or FA allows an increase in the elasticity of
593 composite materials, but also a reduced loss of their elasticity following the aging
594 process ;
595 - increasing the proportion of FA and PVC in can lead to an improvement in the
596 roughness of the surface layer of the composite materials, and this can reduce the
597 amount of impurities or water vapours that can adhere to the surfaces of the
598 materials with positive effects on the operating properties .
599 The researches carried out open new perspectives in the field and thus future researches
600 will aim to optimize the parameters of the composition of composite materials that allow an
601 efficient use of rubber, FA and PVC waste for the obtained of products that can be used in
602 various fields and that have high usage properties .
603

604 Supplementary Materials: Not applicable

605
606 Author Contributions: Conceptualization, DDCM and CSD; methodology, DD, CSD, and
607 CM; software, CM; investigation DD, CSD, M.O. and CM; writing—original draft
608 preparation, DD, CSD, M.O. and CM; writing—review and editing, DD, CSD, and CM All
609 authors have read and agreed to the published version of the manuscript.

610 Funding: Project financed by Lucian Blaga University of Sibiu through the research grant
611 LBUS-IRG-2022-08

612 Institutional Review Board Statement: Not applicable

613 Informed Consent Statement: Not applicable

614 Data Availability Statement: Data available on request.

615 Conflicts of Interest: The authors declare no conflict of interest.

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