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<a href=Composites: Part B 56 (2014) 157–162 Contents lists available at ScienceDirect Composites: Part B journal homepage: www.elsevier .com/locate/compositesb Selective reinforcement of LLDPE components produced by rotational molding with thermoplastic matrix pultruded profiles A. Greco , G. Romano, A. Maffezzoli Department of Innovation Engineering, University of Salento, Via per Arnesano, 73100 Lecce, Italy article info Article history: Received 26 April 2013 Received in revised form 25 June 2013 Accepted 12 August 2013 Available online 21 August 2013 Keywords: A. Glass fibers B. Adhesion E. Pultrusion E. Thermoplastic resin Rotational molding abstract This work is aimed to study the use of pultruded profiles for the selective reinforcement of linear low density polyethylene (LLDPE) parts produced by rotational molding. A preliminary screening on different types of pultruded profiles was performed, highlighting the relevance of adhesion to LLDPE in order to prevent debonding of the reinforcing pultruded profiles. As expected, high density polyethylene (HDPE) matrix pultruded tapes are characterized by a very high adhesion to rotomolded LLDPE. Therefore, HDPE matrix pultruded tapes, fastened on the inner surface of the mold, are incorporated into LLDPE during rotomolding. Plate bending tests performed on reinforced rotomolded plates and pressurization tests per- formed on the box shaped prototypes showed a significant increase of the stiffness with a negligible amount of reinforcement and increase of the weight of the component. 2013 Elsevier Ltd. All rights reserved. 1. Introduction Rotational molding is a process for manufacturing hollow or double-walled plastic products, in the absence of any external pressure. Specific material requirements limit the polymers avail- able for the fabrication of products by rotational molding. In partic- ular, low melt viscosity is required in order to achieve an efficient sintering of polymer powders and void-free products. Further, an adequately high toughness is required in order to allow the extrac- tion of components from molds [1] . Nowadays, only few classes of thermoplastic polymers are processed by rotomolding, and most of them are different grades of polyethylene, in particular linear low density polyethylene (LLDPE). The mechanical properties of these polymers are relatively poor, and rotomolded products find appli- cations in fields where mechanical requirements are not particu- larly critical. Therefore, in recent years, in order to improve the mechanical properties or rotomolded parts, incorporation of nanofillers [2,3] , particulate reinforcements [4,5] or short fibers [6,7] were considered. However, such approaches involve some drawbacks, either in terms of mechanical properties, either in terms of processability. In facts, incorporation of any type of filler is always associated with an embrittlement of the material [8] , as well as with an increase of the viscosity of the polymer melt, which in turn reduces the sinterability of the material, thus increasing the fraction of voids [3,9] . Further, the presence of powders of different size and weight must be carefully managed, ⇑ Corresponding author. Tel.: +39 0832297233. E-mail address: antonio.greco@unisalento.it (A. Greco). 1359-8368/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.compositesb.2013.08.047 in order to avoid segregation, with finer and heavier particles being predominantly dispersed on the outer surface of the rotational molded products, and coarser and lighter particles being located at the inner surface [1,4,10] . Other approaches developed in order to increase the mechanical properties of the rotomolded products involve the use of different types of polymers, such as polyamides [3,11] , polypropylene [12] , high density polyethylene [13] , or com- bination of different materials in multi walled products [14,15] . Recently, it was shown that the rotational molding equipments can be readily adapted to the production of long fiber reinforced composites by the use of thermoplastic prepreg in a bladder mold- ing process [15,16] . Such approach requires pressurization of the mold, and in general, poses severe limitations to the geometric complexity of the part. Further, the glass fibers are uniformly dis- tributed in the rotational molding product, even where loading conditions would not require any reinforcement. On the other hand, pultruded rods are used for the reinforce- ment of polyethylene beams produced by in mold extrusion (or intrusion), in order to optimize the distribution of reinforcement, thus limiting the presence of the glass fibers in the zones of the part which are subjected to higher loads [17] . This involves a reduction of the weight of the components, and of the costs asso- ciated with production, compared to an uniformly distributed rein- forcement. Despite the significant increase of the stiffness of the material, the reinforcement is effective only if high matrix/rein- forcement adhesion occurs. The aim of this work is the production of LLDPE prototypes, reinforced with thermoplastic matrix pultruded profiles, by rota- tional molding. Initially, the adhesion between LLDPE and different " id="pdf-obj-0-5" src="pdf-obj-0-5.jpg">

Contents lists available at ScienceDirect

Composites: Part B

<a href=Composites: Part B 56 (2014) 157–162 Contents lists available at ScienceDirect Composites: Part B journal homepage: www.elsevier .com/locate/compositesb Selective reinforcement of LLDPE components produced by rotational molding with thermoplastic matrix pultruded profiles A. Greco , G. Romano, A. Maffezzoli Department of Innovation Engineering, University of Salento, Via per Arnesano, 73100 Lecce, Italy article info Article history: Received 26 April 2013 Received in revised form 25 June 2013 Accepted 12 August 2013 Available online 21 August 2013 Keywords: A. Glass fibers B. Adhesion E. Pultrusion E. Thermoplastic resin Rotational molding abstract This work is aimed to study the use of pultruded profiles for the selective reinforcement of linear low density polyethylene (LLDPE) parts produced by rotational molding. A preliminary screening on different types of pultruded profiles was performed, highlighting the relevance of adhesion to LLDPE in order to prevent debonding of the reinforcing pultruded profiles. As expected, high density polyethylene (HDPE) matrix pultruded tapes are characterized by a very high adhesion to rotomolded LLDPE. Therefore, HDPE matrix pultruded tapes, fastened on the inner surface of the mold, are incorporated into LLDPE during rotomolding. Plate bending tests performed on reinforced rotomolded plates and pressurization tests per- formed on the box shaped prototypes showed a significant increase of the stiffness with a negligible amount of reinforcement and increase of the weight of the component. 2013 Elsevier Ltd. All rights reserved. 1. Introduction Rotational molding is a process for manufacturing hollow or double-walled plastic products, in the absence of any external pressure. Specific material requirements limit the polymers avail- able for the fabrication of products by rotational molding. In partic- ular, low melt viscosity is required in order to achieve an efficient sintering of polymer powders and void-free products. Further, an adequately high toughness is required in order to allow the extrac- tion of components from molds [1] . Nowadays, only few classes of thermoplastic polymers are processed by rotomolding, and most of them are different grades of polyethylene, in particular linear low density polyethylene (LLDPE). The mechanical properties of these polymers are relatively poor, and rotomolded products find appli- cations in fields where mechanical requirements are not particu- larly critical. Therefore, in recent years, in order to improve the mechanical properties or rotomolded parts, incorporation of nanofillers [2,3] , particulate reinforcements [4,5] or short fibers [6,7] were considered. However, such approaches involve some drawbacks, either in terms of mechanical properties, either in terms of processability. In facts, incorporation of any type of filler is always associated with an embrittlement of the material [8] , as well as with an increase of the viscosity of the polymer melt, which in turn reduces the sinterability of the material, thus increasing the fraction of voids [3,9] . Further, the presence of powders of different size and weight must be carefully managed, ⇑ Corresponding author. Tel.: +39 0832297233. E-mail address: antonio.greco@unisalento.it (A. Greco). 1359-8368/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.compositesb.2013.08.047 in order to avoid segregation, with finer and heavier particles being predominantly dispersed on the outer surface of the rotational molded products, and coarser and lighter particles being located at the inner surface [1,4,10] . Other approaches developed in order to increase the mechanical properties of the rotomolded products involve the use of different types of polymers, such as polyamides [3,11] , polypropylene [12] , high density polyethylene [13] , or com- bination of different materials in multi walled products [14,15] . Recently, it was shown that the rotational molding equipments can be readily adapted to the production of long fiber reinforced composites by the use of thermoplastic prepreg in a bladder mold- ing process [15,16] . Such approach requires pressurization of the mold, and in general, poses severe limitations to the geometric complexity of the part. Further, the glass fibers are uniformly dis- tributed in the rotational molding product, even where loading conditions would not require any reinforcement. On the other hand, pultruded rods are used for the reinforce- ment of polyethylene beams produced by in mold extrusion (or intrusion), in order to optimize the distribution of reinforcement, thus limiting the presence of the glass fibers in the zones of the part which are subjected to higher loads [17] . This involves a reduction of the weight of the components, and of the costs asso- ciated with production, compared to an uniformly distributed rein- forcement. Despite the significant increase of the stiffness of the material, the reinforcement is effective only if high matrix/rein- forcement adhesion occurs. The aim of this work is the production of LLDPE prototypes, reinforced with thermoplastic matrix pultruded profiles, by rota- tional molding. Initially, the adhesion between LLDPE and different " id="pdf-obj-0-16" src="pdf-obj-0-16.jpg">

Selective reinforcement of LLDPE components produced by rotational molding with thermoplastic matrix pultruded profiles

  • A. Greco , G. Romano, A. Maffezzoli

Department of Innovation Engineering, University of Salento, Via per Arnesano, 73100 Lecce, Italy

<a href=Composites: Part B 56 (2014) 157–162 Contents lists available at ScienceDirect Composites: Part B journal homepage: www.elsevier .com/locate/compositesb Selective reinforcement of LLDPE components produced by rotational molding with thermoplastic matrix pultruded profiles A. Greco , G. Romano, A. Maffezzoli Department of Innovation Engineering, University of Salento, Via per Arnesano, 73100 Lecce, Italy article info Article history: Received 26 April 2013 Received in revised form 25 June 2013 Accepted 12 August 2013 Available online 21 August 2013 Keywords: A. Glass fibers B. Adhesion E. Pultrusion E. Thermoplastic resin Rotational molding abstract This work is aimed to study the use of pultruded profiles for the selective reinforcement of linear low density polyethylene (LLDPE) parts produced by rotational molding. A preliminary screening on different types of pultruded profiles was performed, highlighting the relevance of adhesion to LLDPE in order to prevent debonding of the reinforcing pultruded profiles. As expected, high density polyethylene (HDPE) matrix pultruded tapes are characterized by a very high adhesion to rotomolded LLDPE. Therefore, HDPE matrix pultruded tapes, fastened on the inner surface of the mold, are incorporated into LLDPE during rotomolding. Plate bending tests performed on reinforced rotomolded plates and pressurization tests per- formed on the box shaped prototypes showed a significant increase of the stiffness with a negligible amount of reinforcement and increase of the weight of the component. 2013 Elsevier Ltd. All rights reserved. 1. Introduction Rotational molding is a process for manufacturing hollow or double-walled plastic products, in the absence of any external pressure. Specific material requirements limit the polymers avail- able for the fabrication of products by rotational molding. In partic- ular, low melt viscosity is required in order to achieve an efficient sintering of polymer powders and void-free products. Further, an adequately high toughness is required in order to allow the extrac- tion of components from molds [1] . Nowadays, only few classes of thermoplastic polymers are processed by rotomolding, and most of them are different grades of polyethylene, in particular linear low density polyethylene (LLDPE). The mechanical properties of these polymers are relatively poor, and rotomolded products find appli- cations in fields where mechanical requirements are not particu- larly critical. Therefore, in recent years, in order to improve the mechanical properties or rotomolded parts, incorporation of nanofillers [2,3] , particulate reinforcements [4,5] or short fibers [6,7] were considered. However, such approaches involve some drawbacks, either in terms of mechanical properties, either in terms of processability. In facts, incorporation of any type of filler is always associated with an embrittlement of the material [8] , as well as with an increase of the viscosity of the polymer melt, which in turn reduces the sinterability of the material, thus increasing the fraction of voids [3,9] . Further, the presence of powders of different size and weight must be carefully managed, ⇑ Corresponding author. Tel.: +39 0832297233. E-mail address: antonio.greco@unisalento.it (A. Greco). 1359-8368/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.compositesb.2013.08.047 in order to avoid segregation, with finer and heavier particles being predominantly dispersed on the outer surface of the rotational molded products, and coarser and lighter particles being located at the inner surface [1,4,10] . Other approaches developed in order to increase the mechanical properties of the rotomolded products involve the use of different types of polymers, such as polyamides [3,11] , polypropylene [12] , high density polyethylene [13] , or com- bination of different materials in multi walled products [14,15] . Recently, it was shown that the rotational molding equipments can be readily adapted to the production of long fiber reinforced composites by the use of thermoplastic prepreg in a bladder mold- ing process [15,16] . Such approach requires pressurization of the mold, and in general, poses severe limitations to the geometric complexity of the part. Further, the glass fibers are uniformly dis- tributed in the rotational molding product, even where loading conditions would not require any reinforcement. On the other hand, pultruded rods are used for the reinforce- ment of polyethylene beams produced by in mold extrusion (or intrusion), in order to optimize the distribution of reinforcement, thus limiting the presence of the glass fibers in the zones of the part which are subjected to higher loads [17] . This involves a reduction of the weight of the components, and of the costs asso- ciated with production, compared to an uniformly distributed rein- forcement. Despite the significant increase of the stiffness of the material, the reinforcement is effective only if high matrix/rein- forcement adhesion occurs. The aim of this work is the production of LLDPE prototypes, reinforced with thermoplastic matrix pultruded profiles, by rota- tional molding. Initially, the adhesion between LLDPE and different " id="pdf-obj-0-27" src="pdf-obj-0-27.jpg">

article info

Article history:

Received 26 April 2013 Received in revised form 25 June 2013 Accepted 12 August 2013 Available online 21 August 2013

Keywords:

A.

Glass fibers

B.

Adhesion

E.

Pultrusion

E.

Thermoplastic resin

Rotational molding

abstract

This work is aimed to study the use of pultruded profiles for the selective reinforcement of linear low density polyethylene (LLDPE) parts produced by rotational molding. A preliminary screening on different types of pultruded profiles was performed, highlighting the relevance of adhesion to LLDPE in order to prevent debonding of the reinforcing pultruded profiles. As expected, high density polyethylene (HDPE) matrix pultruded tapes are characterized by a very high adhesion to rotomolded LLDPE. Therefore, HDPE

matrix pultruded tapes, fastened on the inner surface of the mold, are incorporated into LLDPE during

rotomolding. Plate bending tests performed on reinforced rotomolded plates and pressurization tests per-

formed on the box shaped prototypes showed a significant increase of the stiffness with a negligible

amount of reinforcement and increase of the weight of the component. 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Rotational molding is a process for manufacturing hollow or double-walled plastic products, in the absence of any external pressure. Specific material requirements limit the polymers avail- able for the fabrication of products by rotational molding. In partic- ular, low melt viscosity is required in order to achieve an efficient sintering of polymer powders and void-free products. Further, an adequately high toughness is required in order to allow the extrac- tion of components from molds [1]. Nowadays, only few classes of thermoplastic polymers are processed by rotomolding, and most of them are different grades of polyethylene, in particular linear low density polyethylene (LLDPE). The mechanical properties of these polymers are relatively poor, and rotomolded products find appli- cations in fields where mechanical requirements are not particu- larly critical. Therefore, in recent years, in order to improve the mechanical properties or rotomolded parts, incorporation of nanofillers [2,3], particulate reinforcements [4,5] or short fibers [6,7] were considered. However, such approaches involve some drawbacks, either in terms of mechanical properties, either in terms of processability. In facts, incorporation of any type of filler is always associated with an embrittlement of the material [8], as well as with an increase of the viscosity of the polymer melt, which in turn reduces the sinterability of the material, thus increasing the fraction of voids [3,9]. Further, the presence of powders of different size and weight must be carefully managed,

Corresponding author. Tel.: +39 0832297233. E-mail address: antonio.greco@unisalento.it (A. Greco).

1359-8368/$ - see front matter 2013 Elsevier Ltd. All rights reserved.

in order to avoid segregation, with finer and heavier particles being predominantly dispersed on the outer surface of the rotational molded products, and coarser and lighter particles being located at the inner surface [1,4,10]. Other approaches developed in order to increase the mechanical properties of the rotomolded products involve the use of different types of polymers, such as polyamides [3,11], polypropylene [12], high density polyethylene [13], or com- bination of different materials in multi walled products [14,15]. Recently, it was shown that the rotational molding equipments can be readily adapted to the production of long fiber reinforced composites by the use of thermoplastic prepreg in a bladder mold- ing process [15,16]. Such approach requires pressurization of the mold, and in general, poses severe limitations to the geometric complexity of the part. Further, the glass fibers are uniformly dis- tributed in the rotational molding product, even where loading conditions would not require any reinforcement. On the other hand, pultruded rods are used for the reinforce- ment of polyethylene beams produced by in mold extrusion (or intrusion), in order to optimize the distribution of reinforcement, thus limiting the presence of the glass fibers in the zones of the part which are subjected to higher loads [17]. This involves a reduction of the weight of the components, and of the costs asso- ciated with production, compared to an uniformly distributed rein- forcement. Despite the significant increase of the stiffness of the material, the reinforcement is effective only if high matrix/rein- forcement adhesion occurs. The aim of this work is the production of LLDPE prototypes, reinforced with thermoplastic matrix pultruded profiles, by rota- tional molding. Initially, the adhesion between LLDPE and different

158

A. Greco et al. / Composites: Part B 56 (2014) 157–162

pultruded profiles was analyzed. Then, box shaped prototypes were built by rotational molding, using HDPE matrix pultruded tapes as reinforcement. The improvement of mechanical properties showed the potential of the developed approach for the production of continuous fiber reinforced LLDPE parts by rotational molding.

2. Materials and methods

The materials used are a linear low density polyethylene (LLDPE), Clearflex RM 50 by Polimeri Europa (Italy), characterized by a density equal to 0.936 g/cm 3 and a melt flow index equal to 4.2 (measured by ASTM D1238). The melting peak temperature, as measured by DCS analysis, is about 129 C. Different pultruded profiles were used for the characterization of adhesion properties to LLDPE and production of rotational mold- ing prototypes:

Thermosetting matrix pultruded rods with circular cross section (kindly supplied by Polystal Composites, Germany) characterized by a nominal diameter of 3 mm, a tensile modulus of 50 GPa, composed of about 85% by weight of glass fibers and 15% vinyl ester matrix. A picture of the rods is reported in Fig. 1. Besides longitudinal fibers, the Polystal rods are also characterized by the presence of helicoidally winded fibers, which are expected to improve the adhesion to LLDPE. Thermoplastic matrix pultruded rods with circular cross sec- tion, kindly provided by Jonam Composites (United Kingdom), characterized by a polypropylene (PP) matrix. The rods have a diameter of 6 mm, and a fiber weight fraction equal to 0.5 (corre- sponding to 0.25 by volume). PP matrix rods are actually made of dry glass bundles surrounded by the PP matrix. The measured ten- sile modulus of pultruded rods is about 6 GPa and the strength is about 120 MPa. Thermoplastic matrix pultruded tapes, with rectangular cross section (0.2 10 mm), supplied by Phoenixx TPC inc (USA). They are characterized by the presence of a high density polyethylene matrix (melting temperature of 127.5 C), a glass fiber weight frac- tion equal to 0.5 (corresponding to 0.25 volume fraction). The mea- sured tensile modulus of the pultruded tapes is equal to 12.4 GPa and the tensile strength is equal to 280 MPa. The higher modulus and strength of the HDPE matrix tapes compared to the PP matrix rods can be explained by the good impregnation of fibers observed in the former case, as evidenced by the SEM images of pultruded tapes, reported in Fig. 2. The adhesion strength of pultruded rods to LLDPE matrix was measured by means of pullout tests. Samples were obtained by a double stage compression molding process, using a Campana hot

158 A. Greco et al. / Composites: Part B 56 (2014) 157–162 pultruded profiles was analyzed.

Fig. 1. Microscopy of thermoset matrix pultruded rod.

158 A. Greco et al. / Composites: Part B 56 (2014) 157–162 pultruded profiles was analyzed.

Fig. 2. Microscopy of HDPE matrix pultruded tape.

press. At first, 20 40 6 mm samples of LLDPE were obtained by compression molding under 200 bar and plate temperature of 30 C, after preheating the material at 180 C. Then, the LLDPE plate was divided in two parts. The rods were enclosed between the two LLDPE plates and compression molded at 200 bar and plate tem- perature of 30 C. Rectangular specimen 20 20 12 mm were obtained. Samples with thermoset matrix rods were obtained after preheating at 170 C, whereas samples with polypropylene matrix rods were obtained after preheating at different temperatures, ranging between 150 and 170 C. In facts, in the case of thermoset matrix rods, the temperature of the process is expected to be of lit- tle relevance, while in the case of the thermoplastic matrix rods, the processing temperature is expected to have a significant influ- ence. Pull-out tests were performed on a Lloyd instruments, series LR5K, according to ASTM D1871-98 standard, using the mentioned rectangular specimens. Each specimen has a single reinforcing rod, which protrudes 30 mm from the cross section area of the plastic mass. The crosshead speed was 50 mm/min. Polyethylene prototypes were built by using a two axes lab scale rotational molding machine designed and produced by Salen- tec srl (Italy). A box-shaped mold was used to fabricate samples characterized by an edge length equal to 148 mm. HDPE matrix pultruded tapes were used for the reinforcement of LLDPE proto- types. The tapes were bonded at the inner surface of the aluminum mold by means of silicon adhesive. One single tape was placed on each of the six square faces of the mold. Then, a standard rotational molding cycle was run using LLDPE powders, setting the oven tem- perature at 280 C, and the rotation speed of the primary and the secondary axes at 6.1 rpm and 1.6 rpm respectively. The mold was held inside the oven for 25 min, after which it was cooled by forced convection in air for about 30 min. A picture of a prototype, including a tape on each face, is reported in Fig. 3a. The prototype is characterized by an average wall thickness equal to 4.2 ± 0.05 mm. A scheme of the side view of each face of the proto- type is reported in Fig. 3b. The mechanical properties of samples extracted from rotomol- ded prototypes were measured by LLOYD LR 5K dynamometer. For characterization purposes, beams were extracted, according to the scheme of Fig. 3b, in correspondence of the red 1 line, and are therefore composed of a stack of LLDPE (about 4 mm thick) and pul- truded strip (about 0.2 mm thick), characterized by a width of 10 mm. Beams were characterized by means of flexural tests, double lap shear tests and short beam tests. Beam flexural tests were performed using a length to thickness ratio equal to 16 and a crosshead speed of 2 mm/min.

1 For interpretation of color in Fig. 3, the reader is referred to the web version of this article.

A. Greco et al. / Composites: Part B 56 (2014) 157–162 4.2 mm LLDPE Pultruded tape
A. Greco et al. / Composites: Part B 56 (2014) 157–162
4.2 mm
LLDPE
Pultruded tape
0.2 mm
(a)
(b)

159

Fig. 3. (a) Photography of reinforced prototype processed by rotational molding and (b) scheme of the side view of each face of the prototype.

Double lap shear tests were used for evaluation of the average adhesion strength between LLDPE and pultruded tapes, by measur- ing the maximum force during the tests:

s A ¼

F max

bh

ð1Þ

where b is the width of the samples and h is the distance between the two laps. Short beam tests were performed according to ASTM D 2344 with a span to thickness ratio equal to 4 and a crosshead speed equal to 0.5 mm/min. Plate bending tests were also performed on the faces extracted from the rotomolded prototypes. Sheets 100 100 mm wide, which, due to the high edge to thickness ratio, can be approxi- mated as thin plates, were simply supported on their perimeter, and loaded with a square punch (16 mm edge) in their center. In reinforced samples, the tape was placed at the extrados. With ref-

Cylindrical duct for water inlet threaded nut polyethylene Flange disk
Cylindrical duct
for water inlet
threaded nut
polyethylene
Flange disk

Fig. 5. Scheme of the connection device for pressurization tests.

part is threaded on its outer surface in order to tighten the LLDPE wall on the disk with a nut.

3. Results and discussion

erence to Fig. 4, being a = b = 90 mm (edge of the plate),

x 1 = y 1 = 37 mm, x 2 = y 2 = 53 mm (edges

of the loading punch), the

A typical force displacement curve obtained by pullout tests of pultruded rods is reported in Fig. 6. In the initial stage of pullout
3 test, the stress is elastically transferred from the rod to the poly-

  • 7 ethylene [18]. The peak in the initial part of the curve corresponds

  • 5 to the break of the adhesive bond between rod and polymer, which takes place when the interfacial shear stress reaches the adhesion strength, s s . As the rod is further pulled out, the load gradually de- creases with the reduction of the contact area between the two components. The measured load at this stage is mainly due to the friction stress acting between rod and polymer. The values of s s can be calculated from Fig. 6. Assuming a uni- form shear stress along the length of rod, the adhesion strength can be obtained from the maximum force F max attained during the test:

ð2Þ

s s ¼

F max

pDL 0

ð3Þ

deflection at a generic point x, y on the plate is given as:

2 X X 4 F senð mpx Þsenð npy Þ 6 mpn mpn npg mpg v
2
X
X
4
F
senð mpx Þsenð npy Þ
6
mpn
mpn
npg
mpg
v ¼
a
b
1
2
1
2
4
cos
cos
cos
cos
p 6 B
2
ðx 2 x 1 Þðy 2 y 1 Þ
a
a
b
b
2
m
m
n
mn
þ n 2
a 2
b 2

where B is the flexural stiffness of the sheet. Finally, the box-shaped prototypes were pressurized by an hydraulic system up to 10 bar. In absence of water leakages, the volume change of the prototype was assumed to be equal to the total volume of water injected inside the prototype. In order to per- form these tests, the prototype was produced by insertion of a con- necting device, according to the sketch of Fig. 5. The connection device is made of a cylindrical duct for water inlet and a flange disk, which is fixed on the surface of the mold at the beginning of the rotational molding process. After processing, the disk remains included in the rotomolded sample wall. The cylindrical

where D is the rod diameter and L 0 is the contact length between

y b y 2 a y 1 x 1 x 2 x
y
b
y 2
a
y 1
x 1
x 2
x

rod and polymer. The adhesion strength calculated by Eq. (3) and

25 F MAX 20 15 10 5 0 02468 displacement (mm) force (N)
25
F MAX
20
15
10
5
0
02468
displacement (mm)
force (N)

Fig. 4. Scheme of the sample geometry and loading device for plate bending tests.

Fig. 6. Force–displacement curve from pull-out tests.

160

A. Greco et al. / Composites: Part B 56 (2014) 157–162

reported in Table 1, indicates that the thermoset matrix rods are characterized by a lower adhesion strength compared to PP matrix rods. The adhesion strength of the latter increases when the pre- heating temperature is increased from 150 to 160 C whereas no relevant difference can be observed heating up to 170 C. This result highlights that full melting of the PP matrix of the rod, occurring only above 160 C, is capable to promote a proper adhesion with LLDPE. A typical force-displacement curve from double lap shear tests is reported in Fig. 7. The adhesion strength between LLDPE and HDPE matrix tape, calculated from the maximum force according to Eq. (1), is 8.4 ± 0.21 MPa. This value is very high, and of the same order of magnitude of the interlaminar shear strength measured for all high density polyethylene composites processed by compression molding [19], despite the fact that that the composite processed by rotational molding is obtained by a virtually zero- pressure process. HDPE matrix tapes are characterized by a much higher adhesion with LLDPE than PP or thermosetting matrix rods (Table 1). Even if thermoset matrix rods are characterized by a higher modulus, and therefore by a higher stiffening potential, debonding at LLDPE/rod interface can be responsible of a loss of the stiffening effect and eventually of yielding of reinforced plates. In contrast, though being characterized by lower modulus, and therefore by a lower stiffening efficiency, the HDPE matrix tapes are likely to pre- serve their stiffening effect even at high values of the applied stress, due their higher adhesion to LLDPE. Therefore pultruded tapes were used for the reinforcement of LLDPE processed by rota- tional molding. A comparison between flexural stress–strain curves of unrein- forced and reinforced beams extracted from rotational molded pro- totypes is reported in Fig. 8. Addition of the HDPE matrix tape involves an increase of the equivalent modulus of the material, from 0.6 ± 0.02 GPa, which is the value of LLDPE, up to 1.2 ± 0.14 GPa. In a previous work [15] it was shown that the flexural stiffness of double wall composites can be efficiently represented by the fol- lowing set of equations:

8 t LLDPE y G;PUL ¼ - 2 y G;LLDPE ¼ t PUL 2 y NA
8
t LLDPE
y G;PUL ¼ -
2
y G;LLDPE ¼ t PUL
2
y NA ¼ 1 - n
t PUL t LLDPE
> > > > > > > > > > > > >
2
< >
t LLDPE þnt PUL
h
i
3
bt
2
LLDPE
þA
ðy
- y
Þ
I LLDPE ¼
LLDPE
>
12
G;LLDPE
NA
h
i
> > >
3
bt
2
PUL
þA ðy
- y
Þ
I PUL ¼
PUL
12
G;PUL
NA
> > > > > > > >
> > : K ¼ X
E i I i ¼E PUL I PUL þE LLDPE I LLDPE
i

ð4Þ

where y G is the position of the baricenter across the thickness of each layer, I the moment of inertia, t the thickness, and A the area, and the pedices LLDPE and PUL refer to LLDPE and pultruded tape. Further, y NA is the neutral axis position across the thickness, n is the ratio between the moduli of pultruded tape and LLDPE, and K is the total flexural stiffness of the beam.

Table 1

Adhesion and friction stresses for thermoset and thermoplastic pultruded rods. In

parentheses the pre-heating temperature.

Rod

s s (MPa)

 

Poystal (170 C)

0.36 ± 0.16

Jonam

(150 C)

1.90 ± 0.68

Jonam

(160 C)

2.52 ± 0.42

Jonam

(170 C)

2.40 ± 0.39

750 double lap shear test 600 450 300 150 0 0.0 0.3 0.6 0.9 1.2 1.5
750
double lap shear test
600
450
300
150
0
0.0
0.3
0.6
0.9
1.2
1.5
displacement (mm)
force (N)

Fig. 7. Force–displacement curve from double lap shear tests.

12 not reinforced reinforced 10 8 6 4 2 0 0.000 0.005 0.010 0.015 strain (mm/mm)
12
not reinforced
reinforced
10
8
6
4
2
0
0.000
0.005
0.010
0.015
strain (mm/mm)
stress (MPa)

Fig. 8. Stress–strain curves from flexural tests on beams extracted from rotational molding prototypes.

Therefore, it is possible to obtain the equivalent modulus of the material as:

E EQ ¼

K

b ðt LLDPE þt PUL Þ 3

12

ð5Þ

Combining Eqs. (4) and (5) with the geometric characteristic of the beam extracted from rotational molded prototypes (b = 10 mm, t PUL = 0.2 mm, t LLDPE = 4.0 mm, E PUL = 12 GPa, and E LLDPE = 0.6 GPa),

an equivalent flexural modulus E EQ = 1.28 GPa was obtained, which

is value in very good agreement with the experimental value.

Short beam tests performed on samples extracted from rota-

tional molded prototypes did not show any deboning at the inter-

face between LLDPE and pultruded tape. On the other hand,

tension break of the pultruded tape was observed for a load value

of about 600 N. In such case, the interlaminar shear stress between LLDPE and pultruded tape can be evaluated to be [15]:

s ¼ 1

b S x;LLDPE

E LLDPE F

2K

ð6Þ

where S x ,LLDPE is the static moment of the LLDPE area with re- spect to the neutral axis, F is the applied force, and K is given by Eq. (4). Combining the geometric characteristic of the beam, for an applied force of 600 N, which is the maximum force attained during short beam tests, it is possible to estimate an interlaminar shear stress equal to 6.4 MPa, in correspondence of tension failure. This value is lower than the adhesion strength measured by double lap shear tests, and explains the absence of any delamination dur- ing short beam shear test. It is worth observing that, in the case that PP or thermoset matrix rods were used, the interlaminar shear stress would exceed the adhesion stress measured by pullout tests (Table 1), causing delamination. The force displacement curve during plate bending tests on sheets extracted from rotational molded prototypes are reported in Fig. 9. From the slope of the force displacement curve, by

A. Greco et al. / Composites: Part B 56 (2014) 157–162

161

inversion of Eq. (2), a flexural stiffness of 3.96 ± 0.15 Nm can be cal- culated for neat LLDPE plates. On the other hand, the flexural stiff- ness for the reinforced plates was calculated as 5 ± 0.15 Nm. Therefore, a stiffening ratio SR = 1.26 was obtained. The results of pressurization tests are reported in Fig. 10. Even in this case, the higher stiffness of reinforced prototype is high- lighted by the lower volume increase. The stiffening ratio (obtained as the ratio between the volume increase measured using neat LLDPE and reinforced LLDPE boxes) is 1.25, very close to the value obtained by plate bending tests. The structural mechanics problem of a reinforced plate subjected to an uniformly applied pressure, was solved by finite element (FEM) software (FlexPDE). For the same lay-up of the reinforcement used for the production of the prototypes, compris- ing one single tape parallel to edges, a stiffness ratio between reinforced and unreinforced plates of 1.22 was calculated. Never- theless, it must be highlighted that more than one reinforcing tape can be used at different positions. For example, by placing two tapes parallel to the square edges, a stiffness equal to 5.3 Nm was estimated by FEM simulation. Two tapes placed on the diagonals of the square face of the rotomolded box yielded a stiffness of 5.8 Nm. Therefore, the use of two tapes in different positions could lead to a stiffness ratio of 1.32 and 1.53, respectively. Such increase of the stiffness of the plate can be obtained by adding a very low amount of glass fibers (about 0.3% by volume for one single tape, 0.6% for two tapes), with a negligible increase of the weight of the component (0.5% and 1% respectively). For comparison purposes, other approaches aimed to increase the stiffness of the rotomolded box are analyzed:

  • (a) Addition of glass spheres to LLDPE.

  • (b) Increase of the thickness of the prototype.

The first approach can be studied by assuming an elastic mod- ulus of 72 GPa for glass and 0.6 GPa for LLDPE. Therefore, the vol- ume fraction of the reinforcing phase required to attain the same stiffness of the plate can be calculated by coupling the Halpin–Tsai model for isotropic material [20] (with an aspect ratio of particles equal to 1) with the expression of the plate bending stiffness, valid for homogeneous materials:

B ¼

Es

3

12ð1 m 2 Þ

ð7Þ

For the three different simulated values (one single tape, two tapes parallel to square edges, and two tapes on the square diago- nal) the corresponding values of the glass spheres volume fraction needed to reach the same stiffness, B, is reported in Table 2. Assuming a LLDPE density of 935 kg/m 3 and a glass density of 2540 kg/m 3 , the corresponding weight increase was obtained.

not reinforced 400 reinforced 300 200 100 0 0246 displacement (mm) force (N)
not reinforced
400
reinforced
300
200
100
0
0246
displacement (mm)
force (N)

Fig. 9. Force displacement curves from plate bending tests on sheets extracted from rotational molding prototypes.

1000 not reinforced reinforced 800 600 400 200 0 0 2 4 6 8 10 pressure
1000
not reinforced
reinforced
800
600
400
200
0
0
2
4
6
8
10
pressure (bar)
volume change (cm 3 )

Fig. 10. Volume change vs pressure from water pressurization tests.

Table 2

Comparison between different approaches for stiffening of rotational molded LLDPE.

 

Pultruded tape

Glass spheres

Thickness

reinforcement

reinforcement

increase

SR

Weight increase

Vf

Weight

Weight

(%)

increase

increase

 

(%)

(%)

One tape

1.23

0.5

0.1

17

7

Two tapes parallel to edges

  • 1.31 0.14 24

1

9.5

Two tapes on the diagonal

  • 1.46 0.21 36

1

15

The values reported in Table 2 are much higher than those ob- tained by using pultruded tapes. Following the second approach, the thickness of the prototype should be increased by a factor of SR 1/3 , as reported in Table 2. In this case, the weight increase would be almost equal to the thick- ness increase. Even in this case the weight increase, though lower than the weight increase estimated for glass spheres reinforce- ment, is much higher than that calculated for the pultruded tapes reinforcement. Besides the increase of the weight of the components, both the alternatives are characterized by severe processing limitations in

rotational molding. The drawbacks of adding glass spheres were al-

ready discussed in the introduction section. Instead, the increase of wall thickness causes higher temperature gradients across wall thickness [21], which in turn involves more severe degradation phenomena on the outer surface of the part, in direct contact with the mold.

4. Conclusions

A new design and processing route was developed for the pro-

duction of reinforced LLDPE components processed by rotational

molding. A preliminary evaluation of the adhesion properties of

different types of pultruded profiles to LLDPE was performed. De-

spite their lower modulus compared to thermosetting matrix pro-

files, thermoplastic matrix profiles are characterized by a higher

adhesion to LLDPE. Further, HDPE matrix tapes were characterized

by an improved adhesion to LLDPE compared to PP matrix rods.

Debonding was not observed between LLDPE and HDPE matrix

tapes even during short beam tests. As a consequence, HDPE ma-

trix tapes were used for the reinforcement of LLDPE prototypes

processed by rotational molding. To this purpose, HDPE matrix tapes were fastened on the inner surface of the mold, before run- ning a standard rotational molding cycle. During processing, melt- ing of LLDPE powders and of HDPE matrix is responsible of the incorporation of the tape in the component walls.

162

A. Greco et al. / Composites: Part B 56 (2014) 157–162

Plate bending tests performed on the faces of prototypes showed that the incorporation of HDPE matrix tapes into LLDPE is responsible of a significant increase of the stiffness, even for very low amount of glass fibers. A similar stiffness increase was ob- tained by pressurization of the box-shaped prototypes. In both cases, it was shown that incorporation of a single tape leads to an increase of the stiffness of about 25%, in good agreement with FEM simulation. Finally, FEM analysis was used for the optimiza- tion of the layout of pultruded tapes on the surface of the box- shaped prototypes. A comparison of different materials choices leading to the same stiffening effect was also proposed, showing the potential of the developed approach for selective reinforce- ment of rotomolded parts.

Acknowledgements

Mr. Francesco Montagna is acknowledged for the support to experimental activity, and Dr. Andrea Salomi for his useful suggestions.

References

[7] Ward J, Panigrahi S, Tabil LG, Crerar WJ, Powell T. Rotational molding of flax fibre reinforced thermoplastics. In: ASAE meeting presentation. Paper No: