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Appl Compos Mater DOI 10.1007/s10443-016-9510-7

Appl Compos Mater DOI 10.1007/s10443-016-9510-7
Appl Compos Mater DOI 10.1007/s10443-016-9510-7
Appl Compos Mater DOI 10.1007/s10443-016-9510-7

Influence of Copper Layer Content in the Elastic and Damping Behavior of Glass-Fiber/ Epoxy-Resin Composites

V.

H. Carneiro 1 & P. Capela 1 & J. C. Teixeira 1 & S. Teixeira 2 &

F.

Cerqueira 3 & F. Macedo 3 &

L. Ribas 4 & D. Soares 1

Received: 2 May 2016 /Accepted: 1 June 2016 # Springer Science+Business Media Dordrecht 2016

Abstract The impact in the elastic behavior and internal friction, caused by the introduction of Copper layers in Glass-Fiber/Epoxy Resin composites and temperature effects, were studied and evaluated recurring to Dynamic Mechanical Analysis. It is shown that the introduction of Copper layers increases the storage modulus of the composites and delays their glass transition temperature, however, it allows a faster transformation. Additionally, it is concluded that the introduction of Copper layers elevates the internal friction during the glass transition phase by the inversion of the deformation mechanism due to thermal expansion and increase in the Poissons ratio of the epoxy resin to a value near 0.5 where its deformation is approximately isochoric. This increase in damping capacity is relevant in application with cyclic fatigue and mechanical vibration.

Keywords DMA . Composite materials . Elastic properties . Electronic materials . Viscoelasticity

1 Introduction

A typical use of glass-fiber/epoxy-resin composites is in the fabrication of printed circuit boards (PCB) for electronic applications [1], due to their good relation between mechanical

* V. H. Carneiro vitorhcarneiro@hotmail.com

1 Department of Mechanical Engineering, University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal

2 Department of Production and System Engineering, University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal

3 Physics Center, University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal

4 Bosch Car Multimedia, Braga, Portugal

Center, University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal 4 Bosch Car Multimedia, Braga, Portugal

Appl Compos Mater

strength, stiffness, electrical and dielectric insulating properties [2]. In this kind of application, bundles of continuous silica based (Si0 2 ) amorphous glass-fibers (GF) are woven to form a layer [3]. A defined amount of these layers are then stacked and impregnated with thermoset epoxy-resin (ER) which is posteriorly cured to obtain the final composite plate [4], generally denominated by FR-4. Additionally, copper (Cu) layers may be introduced in the manufactur- ing to fix and drive electrical current where the electronic components are presented. The number and distribution of these layers can change according to the land pattern of specific applications, although the thickness of the FR-4 plate usually remains constant. This implies that the amount of GF and ER is not the same and this has a direct influence in the overall mechanical performance of such composites. The macroscopic elastic behavior of these composites can be defined by their deformation behavior. Given that the volume fractions of the materials used in the composites may change, then, it is crucial to evaluate this modification in the overall mechanical behavior. Additionally, these materials are frequently subjected to variations in temperature (during the soldering process and also in service), which will influence their performance and deformation behavior. The present study, devotes to the characterization of the in-plane thermoelastic behavior of these composites by the introduction of Cu layers. As a result, values of the storage modulus (E) and the internal friction (Q 1 ) in the absence of Cu layers, and in the presence of one and six Cu layers are determined and discussed. These values, will give a step forward for the correct dimensioning of the composites and to determine/estimate their deformation behavior in real applications. Additionally, it is shown that the introduction of Cu layers may be benefic to increase the damping capacity in these composites and enhance their behavior in cyclic loading and vibration situations.

2 Experimental Procedure

Unsoldered FR-4 plates (Panasonic Laminate R-1566) are the base materials to be tested in the presented study. Rectangular specimens, (2 × 1.2 × 30) mm 3 , were manufactured using a diamond grinding wheel oriented in the parallel alignment of the glass fibers. To determine their thermomechanical behavior, the samples were tested using Dynamic Mechanical Anal- ysis (DMA - TA Instruments Q800) technique in tensile testing configuration. This type of test applies a sinusoidal load to the sample and monitors the resulting deformation, evaluating the accumulated energy in the material (E’ – Storage modulus) and the one that is lost in that process (E^ Loss Modulus) [5]. Consequently, the damping capacity of the material can be achieved determining the Internal friction (Q 1 ), applying Eq. 1 [6].

Q 1 ¼ tanðδ Þ¼ E E 0

ð1 Þ

An initial pre-load of 4.5 N was applied to each sample to ensure that there was a permanent tensile effort, while they are subjected to a 1.5 μm constant amplitude at 1 Hz. To evaluate the thermal effects in the samples behavior, a temperature ramp was defined: a heating rate of 3 °C/min from room temperature (RT) to up to 250 °C, in an inert nitrogen atmosphere. The dynamic weight loss in reference samples was determined by Thermogravimetric Analysis (TGA) using a TA Instruments SDT 2960, with a heating rate of 10 °C/min, up to 700 °C, under an atmosphere of air (constant flow of dry air).

SDT 2960, with a heating rate of 10 °C/min, up to 700 °C, under an atmosphere

Appl Compos Mater

3 Results and Discussion

Figure 1a, b and c shows optical images (magnified) of the samples with none, one and six Cu layers, respectively, in which the absence and distribution (in the case of their presence) of Cu layers may be observed. Sample a (with no Cu layer) is characterized by eight layers of GF, and the same is verified in the case of one Cu layer sample. However, in the six Cu layers sample, the number of GF layers is reduced to four. Figure 1 d shows the relative weight of samples with none (Sample a), one (Sample b) and six Cu (Sample c) layers obtained by TGA measurements. Since at 700 °C both Cu layers and GF that compose the samples remain in their original solid state, the observed weight decrease must be related with degradation of the ER component. The transition is initiated at (the manufacturer points 350 °C as the decomposition temper- ature). Thus, it can be determined that the ER s relative weight (W ER% ) in samples a, b and c is respectively 39.80, 33.04 and 20.53 % of the total initial samples weight. As expected, given that the overall plate thickness is maintained across all Cu content, there is a reduction in the ER content as the amount of Cu is increased. Additionally, the increase in total relative weight (W % ), for temperatures above 600 °C, only observed in samples with Cu layers, can be justified by the Cu oxidation and the formation of Cu 2 O and CuO compounds [ 7 ] Fig. 2 . Based on Fig. 1, the height of the Cu layers (H Cu ) and overall sample (H Sample ) can be determined. Thus, knowing the density of Cu (ρ Cu ), GF (ρ GF ) and ER (ρ ER ) and the relative weights of Cu (W Cu% ), GF (W GF% ), ER (W ER% ) of the reference samples submitted to TGA at 600 °C (W 600 °C ), the volume fraction of the materials (V Cu% , V GF% and V ER% ) can be determined using Eqs.2 to 6. The results of the referred determinations, for samples a, b and c, are summarized in Table 1.

for samples a, b and c, are summarized in Table 1 . Fig. 1 Optical images

Fig. 1 Optical images of samples a, b and c profile with, respectively, none, one, and six Cu layers

in Table 1 . Fig. 1 Optical images of samples a, b and c profile with,

Appl Compos Mater

Appl Compos Mater Fig. 2 TGA curves of the samples, representing the relative weight as a

Fig. 2 TGA curves of the samples, representing the relative weight as a function of temperature caused by ER loss

W Cu% ¼

V cu%

H cu

H Sample

W GF% ¼ W 600 ½

C W C u %

V Cu%

W ER%

þ

W

600

½ c

 
     
 

ρ

ER

 

ρ

GF

W ER% þ W 600

½ c

þ W Cu%

1

1

ρ

ER

ρ

GF

ρ

Cu

ρ

GF

Table 1 Sample base material quantification

ð2 Þ

ð3 Þ

ð4 Þ

Sample

a

b

c

N° of GF Layers

8

8

4

N° of Cu Layers

0

1

6

Cu total Thickness, H Cu [μm]

0

35

170

Volume Fraction [%]

ER

54.54

47.25

44.16

GF

45.47

49.63

40.67

Cu

0.00

3.13

15.18

Appl Compos Mater

V ER% ¼

V GF% ¼

W ER%

ρ

ER

W ER% þ W 600

½

c

ρ

ER

ρ

GF

W 600

½

þ W Cu%

c W Cu%

ρ

GF

1

ρ

Cu

1

ρ

GF

W ER% þ W 600

½

c

ρ

ER

ρ

GF

þ W Cu%

1

ρ

Cu

1

ρ

GF

ð5 Þ

ð6 Þ

Based on the results obtained by TGA and by the previous deduction, the theoretical apparent Youngs modulus (E) of the samples, may be determined by the classic rule of mixtures and employing Eq.7.

E ¼ E FR4

ð V

GF

þ

V

ER

Þþ E Cu V Cu

ð7 Þ

Where E FR-4 and E Cu are, respectively, the Youngs modulus at RT of the FR-4 and Cu layers of the composite. According to Eq. 7, as Cu layers are introduced in the composite and the volume fraction of FR-4 decreases, it is expected that there is an increase in the stiffness of the composite. Thus, the expected values of Youngs modulus for samples without, with one and six layers of Cu are respectively, 17 (according to the manufacturer), 19.91 and 31.12 GPa (determined by the rule of mixtures). These results may be observed and compared in Table 3. Figure 3 show the temperature dependent Eof the samples shown in Fig. 1. In terms of elastic behavior, it can be observed that the values of the macroscopic Eof the samples without Cu are lower than the ones that have Cu layers. At RT, it may be observed that the content of Cu is the main cause in the increase of the Eof the sample, as it assumes the values of 17.28, 20.85 and 30.00 GPa, respectively, for samples a, b and c. These values tend to decrease, with an approximately constant slope for all samples, as the temperature is increase until Tg, and this determines that the introduction of Cu content results in a proportional increase in Euntil such temperature is reached. Until the Tg, the polymer molecules are restricted and there is an apparent glassy behavior [12]. However, when this temperature is reached, the ER part of the composites begins to change their free volume, has the amorphous matter generates a coordination large scale polymer chain motion and the stiff samples are transformed to a rubbery state. It may also be observed that the predictions determined by Eq.7, using the rule of mixtures, present a good correlation with the experimental results. The values of Tg in the tested samples were obtained using the classic interception of the tangents of the glassy state and rubbery transition slopes, according to the standards ASTM E1640 and DIN EN 61006 [13]. It may be observed that the introduction of Cu layers causes an increase in the Tg, as the samples a, b and c, respectively, present a Tg of 144, 172 and 179 °C It is known that the value of Tg is directly correlated to the polymer molecular weight between entanglements (M e ). However, on an initial phase, only some cross-links are ther- mally activated, the delay in the transition in samples with Cu is justified by the insulation effect that the Cu layers represent in the exterior of the samples. In fact, in samples with no Cu layers, convection heat currents start to activate the ER in the exterior of the samples and this heat is later conducted to the interior of the sample, promoting an earlier thermal activation of

of the samples and this heat is later conducted to the interior of the sample, promoting

Appl Compos Mater

Appl Compos Mater Fig. 3 Storage modulus of the samples obtained by DMA, as a function

Fig. 3 Storage modulus of the samples obtained by DMA, as a function of temperature

the samples. In samples with Cu layers in their surfaces, these convection heat currents start to affects the Cu layers firstly, and only then the heat is conducted to the internal ER layers. However, once the Cu layers are heated, and given their superior thermal conductivity (Table 2), in time the heat will flow better to the interior of the sample, thus promoting cross-linking by thermal activation and a quicker rubbery transformation due to the propor- tional relation between M e , temperature (T) and storage modulus (E) represented in Eq. 8. Where ρ is the density of the polymer (in the case ER), R is the gas constant and Φ is a factor used to correct unreacted free chain ends, defined as the ratio between the mean square end-to- end distance in the networking of chains and the length of a randomly coiled chain [14].

E 0 ¼ ΦρRT

3 M e

ð8 Þ

This fact may be confirmed in Fig. 3, by the increase in the slopes and consequently the rate of transformation in the transition phase for samples with Cu layers and moreover confirmed in Fig. 4 that represents the evolution in the internal friction (Q 1 ) in the samples as the temperature is increased.

Table 2 Base materials thermo-mechanical properties

Material Density, ρ [kg/m 3 ]

CTE, α [×10 6 /°C] Youngs Modulus (RT), E [GPa]

Poissons ratio, ν []

Thermal

Conductivity,

 

k [W/m°C]

FR-4

ER 1400 [8] GF 2540 [8]

11.0 [9]

17

0.113

0.25

Cu

8960 [9]

16.7 [10]

110

at RT: 0.345 [11] at 250 [°C]: 0.350 [11]

398.00 [10]

Appl Compos Mater

Appl Compos Mater Fig. 4 Internal friction of the samples obtained by DMA, as a function

Fig. 4 Internal friction of the samples obtained by DMA, as a function of temperature

At RT, it may be observed that there is a tendency to increase the internal friction in the samples as layers of Cu are introduced. It is shown that the values of Q 1 , for samples without, with one and six layers of Cu is respectively, 0.0089, 0.0106 and 0.116 (these values may be compared in Table 3). This fact implies that the introduction of Cu layers, although makes the overall composite more rigid, it also increases its damping capacity. Given that one common application of these composites is in PCB industries, these characteristics may be benefic to reduce the cyclic fatigue and vibration in surface mounted components and increase the life expectancy on these kind of products. Even though the delay of the peaks in samples with Cu content may be attributed by thermal convection and conduction, there is also a variation of their values in terms of internal friction. It may be observed that the maximum values of internal friction in the samples a, b and c, are respectively, 0.060, 0.121 and 0.085. This change in the peak value and enhance- ment of internal friction by the introduction of Cu layers may be attributed to two distinct mechanism originated by the increase in temperature: i) the mismatch of CTEs of the FR-4 and Cu layers; ii) the change of the Poissons ratio in the ER. In the samples with no Cu content, as their solicited by the sinusoidal load of the dynamic mechanical analysis (Sample a - Fig. 5a), the deformation by Poissons Effect and in-plane expansion is uniform as the layers of GF/ER are fairly isotropic for the full range of temperatures. Any thermally activated transformation in material properties is uniform in the

Table 3 Theoretical and Experimental sample properties obtained by DMA

Sample E - Theoretical (RT) [GPa]

E’ – Experimental (RT) [GPa]

Tg [°C]

tan δ at RT []

tan δ at Peak []

a 17.00

17.28

144

0.0089

0.0600

b 19.91

20.85

172

0.0106

0.1210

c 31.12

30.00

179

0.0116

0.0850

Appl Compos Mater

Appl Compos Mater Fig. 5 Graphical representation of the samples being submitted to a tensile load

Fig. 5 Graphical representation of the samples being submitted to a tensile load

composite. However, for samples with Cu content, as temperatures rises the Cu layers will expand more than the FR-4 layers (samples b and c Figs. 5b,c), given their more elevated CTE (Table 2). This increase in internal friction is more evident for samples with non- symmetrical distribution of Cu layers (Sample b Fig.5b). The increased expansion of the Cu layer in one face of the plate, destabilizes the equilibrium of the composite during the dynamic tensile load, which implies an increase in internal friction. Additionally, as the temperature is risen, there is a change in the ER morphology that is not accompanied by the Cu layers. While the Cu layers maintain a certain stability of their Poissons ratio for the tested temperature span (from 0.345 at RT to 0.35 at 250 °C), this cannot be said for the FR-4. The latter, while at RT has a Poissons ratio of 0.113. Has the temperature rises, and due to the transformation from a hard solid to a rubbery state, the Youngs and Shear moduli of its ER start to decrease and the material itself start exhibiting an isochoric behavior. Thus, after the post-Tg transformation in ended, the ER has a Poissons ratio that approaches a value of 0.5. Thus at RT, due to the Poissons effect, the Cu layers will contract more than the FR-4 layers with ER (Fig. 6a), while ate 250 °C there will be an opposite behavior (Fig. 6b).

ate 250 °C there will be an opposite behavior (Fig. 6 b). Fig. 6 Schematic representation

Fig. 6 Schematic representation of the inversion of the Poissons effect caused by the increase of temperature

6 b). Fig. 6 Schematic representation of the inversion of the Poisson ’ s effect caused

Appl Compos Mater

Appl Compos Mater Fig. 7 Inversion of bending direction by the increase of the ER Poisson

Fig. 7 Inversion of bending direction by the increase of the ER Poissons ratio in Sample b when temperature increases

This change in the Poisson s ratio generates a transition phase in the deformation behavior of the samples with Cu layers. In the samples with one layers of Cu (Sample b), the Poisson s ratio of the ER at RT is lower than the same elastic constant of the Cu layers, and the sinusoidal tensile load generate a bending effect where the outside face is the one with the Cu layer (Fig. 7 a). As this transition occurs when the ER reaches its Tg and its Poisson s ratio increases, the bending orientation will be inverted (Fig. 7 b) and this overall process will enhance the dissipation of mechanical energy within the samples and consequently the internal friction will be risen. Simultaneously, a higher degree of deformation is achieved on the surface constituted by the ER (without the Cu layer) at elevated temperatures. These effects combined can explain the increase on the peak value of internal friction (Q 1 = 0.121) on samples with one Cu layer. In the sample with six Cu layers, this transition in the ER also occurs, however, given that their distribution is symmetric along the middle plane of the plate, there is no bending in the sample and consequent ly no change in the bending direction. However, there is still a change in the overall Poisson s effect in the sample. At RT, this effect is more pronounced for the Cu layers, as it Poisson s ratio is more elevated than the ER of the FR-4 layers (Fig. 8 a). When the temperature is increased above the Tg, the Poisson s effect will be enhanced in the ER, and it s overall deformation will be more relevant than in the Cu layers (Fig. 8 b). Thus, this transition will cause an increase in the internal frict ion of the samples that, although given the balance within the samples, will be less relevant than in non-symmetrical samples (Sample b).

Fig. 8 Inversion of the Poissons effect by the increase of the ER Poissons ratio in Sample c when temperature increases

Inversion of the Poisson ’ s effect by the increase of the ER Poisson ’ s

Appl Compos Mater

4 Conclusions

In this study it is shown that the content of Cu layers in GF/ER composites influences their overall mechanical behavior. An increase in the Cu volume fraction implies an increase on both macroscopic Eand Tg of these composites, by the increase in rigidity of the layers and their isolation effect that delays the initial cross-link activation and a posterior acceleration of the rubbery transition by their superior thermal conductivity. Additionally, it is shown that the introduction of Cu layers generates an increase in the samples internal friction by two distinct mechanism: the mismatch of CTEs between the Cu and FR-4 layers; the increase of the Poissons ratio of the ER after Tg transition. It is also shown, that the introduction of Cu layers in an asymmetric geometry (relatively to the middle plane of the plate) further increases the damping capacity in the samples, which may be benefic in situations of cyclic loading and mechanical vibration.

Acknowledgments The authors acknowledge the financial support provided through project SI I&DT projeto em co-promoção n° 36265/2013 (Projeto HMIEXCEL 2013-2015).

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