U. Kalsooma,
A. Peristyya,
P. N. Nesterenkoab and
B. Paull*ab
aAustralian Centre for Research on Separation Science (ACROSS), School of Physical Sciences Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia. E-mail: brett.paull@utas.edu.au
bARC Centre of Excellence for Electromaterials Science (ACES), School of Physical Sciences Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia
First published on 8th April 2016
The development of a thermally conducting composite material that can be rapidly 3D printed into prototype objects is presented. The composite structures containing 10, 20, 25 and 30% (w/v) of 2–4 micron sized synthetic diamond microparticles added to the acrylate polymer were produced using a low cost stereolithographic 3D printer. The prepared materials were characterised according to heat transfer rates, thermal expansion co-efficients and contact angles, and analysed using high resolution electron microscopy, thermogravimetric analysis and thermal imaging. The composites displayed minor enhancements in heat transfer rates with incrementing diamond content upto 25% (w/v), however a significant improvement was observed for the 30% (w/v) polymer–diamond composite, based on an interconnected diamond aggregate network, as confirmed by high resolution scanning electron microscopy. The developed material was used in the fabrication of prototype 3D printed heat sinks and cooling coils for thermal management applications in electronic and fluidic devices. Infrared thermal imaging performed on 3D printed objects verified the superior performance of the composite compared to the inherent polymer.
The need for a wider variety of materials demonstrating enhanced thermal properties has led to the development of polymer composite systems,6–8 that adequately combine the processability and weight/strength properties of the original polymer,9 with the additional thermal conducting properties of the fillers.10,11 Ceramic fillers e.g. alumina (Al2O3), and silicon carbide (SiC),10,12 and carbon-based materials, such as graphite13 and diamonds14 have all been previously used for the formation of thermally conducting composites, based upon their excellent thermal properties. Among these various fillers, diamond exhibits the highest thermal conductivity [2200 W m−1 K−1]15 and mechanical stability, and therefore can be considered as a very promising filler for improving the thermal conductivity of future polymer composites.
There are two types of synthetic diamond powders, namely nanodiamonds and microdiamonds, which can be used as fillers in polymer composites. Detonation nanodiamond powder (DND) is manufactured by detonation synthesis in large quantities and is a comparatively low cost nanocarbon material for a wide range of potential applications, including composites.16 However, the use of microdiamonds, synthesised at high temperatures and high pressures (HPHT diamond), when used as fillers have proven more successful in increasing the thermal conductivity of the resultant composites.17,18 In recent years the development of polymer composites using diamond powder (containing DND or micro sized HPHT particles) has been the subject of several studies.1,16,19–22 For example, Zhang et al. developed epoxy composites using diamond powder, and applied the resultant materials to electronic packaging.19 A composite containing 68% volume loading of diamond powder was shown to exhibit superior thermal properties (thermal conductivity = 4.1 W m−1 K−1) as compared to the starting epoxy polymer itself (thermal conductivity < 1 W m−1 K−1). Similar studies using low density polyethylene and polypropylene diamond powder composites have also been reported.23,24
In the majority of the above studies, the polymer–diamond (PD) composites have been produced using a traditional basic casting method. Typically an aqueous suspension of diamond or diamond powder is directly added to the polymer solution25 and stirred magnetically, followed by sonication for several hours. The polymer diamond suspension is then cast into stainless steel moulds and cured at room temp or via heating.26,27 Clearly, such traditional fabrication methods are time consuming (as the curing of the polymer can sometimes take up to several days)26 and labour-intensive. Such techniques are certainly not amenable to the introduction of complex internal structures28 or rapid prototyping.
Over the past decade 3D printing has established itself as a technique of choice for rapid casting/prototyping of polymer objects/devices.29 3D printing facilitates the production of complex three dimensional objects with internal structure, and increasing resolution (typically 50–500 μm in modern low cost printers). Using this mould free technology and freely available CAD drawing software, rapid alterations in the preform geometries and dimensions can be made iteratively and on-demand.30,31 More recently 3D printing is being explored for the production of composite based objects.32–34 A significant body of work on 3D printing of tricalcium phosphate containing composites has been reported, with a variety of bulk materials, to improve strength, biocompatibility and porosity of the material, for use as bone scaffolds for biomedical applications.35–38 Additionally there are a limited number of reports in which 3D printing has been employed to produce polymer composite materials exhibiting enhanced optical,32,34 electrical33,39 and thermal properties.40
Recently, carbon base composites amenable to 3D printing have received considerable attention. For example, conductive carbon black was recently used as a filler for printing a conductive thermoplastic composite using a low-cost 3D printer.33 In this case the composite material was used for the rapid fabrication of a variety of functional electronic sensors, including piezoresistive sensors capable of sensing mechanical flexing and capacitive sensors printed with the ability to sense the presence and volume of liquids. More recently, a report on 3D printing of a new thermally conducting polymer composite achieved through the introduction of graphene flakes into acrylonitrile–butadiene–styrene (ABS) has been published.40 In this work, graphene oxide was added to the ABS followed by chemical reduction of the filler to form graphene sheets. The dispersion containing graphene and polymer was precipitated in the presence of deionised water. The developed composite was melted (210 °C) within the 3D printer nozzle, a process known as fused deposition modelling (FDM), for the production of the thermally conducting composites. However, using the FDM process it was not possible to introduce high filler concentrations, as the formation of graphene aggregates was reported at 7.4 wt%, which resulted in blocking of the printer's nozzle.40
An exciting alternative approach, which completely avoids the limitations of the FDM based printers for composite production, is stereolithography. In stereolithographic 3D printers, a laser moves along the surface of the liquid polymer (composite phase), curing the polymer layer by layer, until the entire structure is completed.41 Here there are no nozzles or spray devices likely to experience blockages, and provided the composite suspension is stable and the photopolymerisation process uninhibited, a large variety of composite materials can be readily produced.
In the following paper we report for the first time the 3D printing of a novel, low-cost thermally conductive composite material, based upon commercially available resins for stereolithographic 3D printers and microdiamond particles. The composite material was developed by simply suspending the HPHT diamond microparticles within the commercial acrylate based resin at concentrations as high as 30% (w/v), avoiding any additional chemical reactions or further modifications. The acrylate polymer–diamond suspension was directly introduced into the printer and used for the fabrication of thermally conducting objects to demonstrate potential applications in thermal management in electronic and fluidic devices.
Miicraft cream resin (BV-001) was used for the formation of composites. Acrylate polymer diamond composites (APD-X, where “X” represents diamond powder concentration) consisting of 10%, 20%, 25% and 30% (w/v) microdiamond concentrations were prepared by adding the appropriate amount of powder to the resin. The APD-X mixture was stirred for an hour vigorously with a magnetic stirrer to promote homogeneous dispersion of the particles. This APD-X mixture was then sonicated for 30 min to further disperse the diamond microparticles in the resin. Once prepared the resin consisting of diamond microparticles was used as such without further modifications.
For characterisation, rectangular blocks (l = 23 mm, w = 23 mm, h = 10 mm) of AP and APD composite consisting of 10, 20, 25 and 30% (w/v) diamond powder were fabricated.
The difference in initial and final length was measured using the Image J software. To make the equipment suitable for Image J software, the scale (mm) was placed on the heating unit. The distance in pixels was converted to millimetres using the scale and change in length (ΔL) was measured. The linear thermal expansion coefficient was measured using the following formula
α = ΔL/(Lo/ΔT), |
Initially, the maximum concentration of diamond suspension in the resin whilst remaining suitable for printing was investigated. Above 30% (w/v) microdiamond concentration, poor adhesion of the material with the printer's stage was observed and so limited the diamond content above this concentration.
Printed AP and APD composite rectangular bars (l = 23 mm, w = 23 mm, h = 10 mm) consisting of various concentrations of diamond microparticles ranging from 10–30% were investigated according to their heat transfer efficiency. Each block was tightly held in direct contact with the heating system set at 20 °C and a thermocouple was placed at the top surface of the block to observe temperature changes. The temperature of the heating system was raised to 100 °C (the system required only few seconds to get to that temperature) and time taken to heat the top surface of 3D printed block from room to target temperatures (up to 60 °C) was recorded. Fig. 1 shows a plot of time vs. top surface temperature for APD composite bars consisting of various concentrations of diamond particles. As shown the ability of the composite to transfer heat increases slightly with an increase in microdiamond concentration up to 25% (w/v). However, as the diamond concentration was increased to 30% (w/v), a significant improvement in the heat transfer rate of the composite was noticed, requiring only ∼30% of the time for the top surface of the block to reach the target temperature (i.e. 60 °C), as compared to the lesser composites. This significant increase in the heat transfer efficiency for the APD-30 composite results from the formation of interconnected diamond microparticle aggregates at concentrations above 30%, as has been demonstrated previously for traditionally cast polymer composite materials.8
Fig. 1 A plot of time taken with bottom heated 10 mm AP and APD composite blocks for the top surface to rise from 20 °C to target temperatures (25, 30, 35, 40, 45, 50, 55 and 60 °C). |
To understand this behaviour and distribution of diamond microparticles, SEM images of the AP and APD composites were taken. High resolution images of the 3D printed diamond–polymer composite materials with increasing concentrations of diamond particles are shown in Fig. 2. SEM images of the APD-10 composite showed that most of the diamond particles were isolated from each other (Fig. 2b) and this limited contact between microparticles resulting in poor heat transfer capability. However, SEM images of APD-20 and APD-25 (Fig. 2c and d) composites showed a slight improvement in contact between the particles, reflected in small increments in heat transfer efficiency. High resolution images of APD-30 displayed a drastic increase in a number of contact points between the microparticles, showing the formation of highly interconnected diamond aggregates (Fig. 2e and f). This highly connected network of diamond microparticles resulted in the substantial (greater than 200%) improvement in the heat transfer efficiency of the composite.
Fig. 2 SEM images taken from a cross-section of (a) AP (b) APD-10 (c) APD-20 (d) APD-25, and (e)–(f) APD-30 composite materials. |
This behaviour of formation of cluster–cluster network has been described previously for carbon based fillers. The conductive particles form aggregates in the composite at relatively low filler contents. As the concentration of filler is increased, the number and size of the clusters increases and above a critical filler concentration, known as percolation threshold, these clusters begin to accumulate in floccules, forming a highly interconnecting network of particles filling the entire volume of the polymer and thus making the material conductive.44
This threshold is evident when plotting the relationship between heating time required to raise the composite temperature from 20 to 50 °C vs. diamond particle concentrations (Fig. 3). Fig. 3 shows significant drop in heating time above 25% (w/v), thus providing evidence for the presence of a fully interconnected network of diamond particles above this concentration.
Fig. 3 Plot of heating time required for raising the block temperature from 20 to 50 °C vs. concentration of diamond particles in the APD composite. |
The TGA curve for the APD-30 composite showed significantly different profiles compared to AP. In the first step a small weight loss (6%) occurred once again due to water. In the second step between 300 and 400 °C 19% of the weight was lost, compared to 22% for AP, which is because of the reduced volume of the polymer in the composite. Above 400 °C, the weight of the sample again decreased rapidly, from the degradation of the composite backbone i.e. AP leaving only. However, the decomposition of the AP continued slowly until 500 °C, leaving only 46% of the sample weight which included the diamond particles residue itself. The TGA curve for the APD-30 composite demonstrated that in this case the thermal stability of the original polymer in air remains unaffected by the addition of diamond microparticles. These results suggested that diamond microparticles are present in the form of a suspension in the resin which does not significantly affect the chemical structure of the resin and therefore its overall thermal stability.
Diamond concentration w/v (%) | Average (n = 3) apparent contact angle (θ) |
---|---|
0 (AP) | 52.5 ± 2.1 |
APD-10 | 85.9 ± 2.2 |
APD-20 | 94.6 ± 3.1 |
APD-30 | 98.7 ± 2.4 |
The results obtained showed how the contact angle kept increasing with an increase in diamond particle concentration in the composite. As the surface of diamond is actually known to be rather hydrophilic rather than hydrophobic, these contact angle measurements are more likely to be a surface roughness effect. It is known that surface roughness will enhance the wettability caused by the chemistry of the surface. In this case the diamond increases the surface roughness (as shown by the SEM images in Fig. 2), but the vast majority of the diamond is beneath a thin surface polymer coating which masks the native hydrophilicity of the diamond particles. Thus in this case it's the hydrophobic properties of the acrylate polymer that are enhanced by the increased surface roughness. These results are in agreement with a previous report on diamond polymer composite where an increase in filler concentration resulted in an increase in apparent contact angles.16
To evaluate the effect of inclusion of the microdiamond particles on the thermal stability of the 3D printed composite, the LTECs for both the AP and APD-30 composite were determined. The LTEC of diamond itself is 1.18 × 10−6 K−1. Temperature of the AP and APD composite was raised from 20 °C to 45 °C and lengths of the AP and APD-30 composite blocks at both temperatures were measured (Fig. 6). The LTEC value for the polymer was measured to be 180 × 10−6 (±2.4 × 10−6) K−1 which falls within the LTEC range previously reported for similar polymers.50 The inclusion of diamond particles reduced the LTEC value to 48 × 10−6 (±3.6 × 10−6) K−1 for APD-30, representing a significant reduction. This observation is in line with many previous studies on composite materials which have shown that an increase in the concentrations of fillers within polymer matrices can reduce LTECs, as the uniform distribution of the particles within the matrix disrupts the expansion of the polymer chains at high temperature.50
Table 2 compares these values with a number of metal and polymer materials. The table highlights how the introduction of the 30% diamond microparticles shifts the LTEC of the composite considerably away from typical polymer values towards values more commonly associated with metal and metal alloys.
Material | LTEC (×10−6) K−1 |
---|---|
Synthetic diamond | 1.1–1.2 |
Silicon carbide | 3.8 |
Gallium arsenide | 5.9 |
Copper | 16.5 |
Silver | 19.8 |
Aluminium | 22 |
Polytetrafluoroethylene (PTFE) | 70–200 |
High density polyethylene (HDPE) | 60–110 |
Polymethylmethacrylate (acrylic) (PMMA) | 50–90 |
Miicraft cream BV-001 resin (AP) | 180 |
AP–diamond composite (APD-30) | 48 |
A heating system (as described earlier in the Heat transfer measurement section of the Experimental) was set at 100 °C and used to evaluate the heat transfer performance of the printed sinks. The difference in temperatures and heat distribution of the heat sink printed from the basic AP resin and the APD composite material, each heated for 10 min, was determined using a thermal imaging camera. Thermal images of the two printed heat sinks are given in Fig. 7c and d. Both objects were heated for 10 min and temperatures recorded at three exact positions (i.e. top, middle and bottom as shown within the figure). The IR images for the AP and APD-30 composite heat sinks showed that the temperature of the composite heat sink was almost 5–8 °C higher for all three regions (i.e. top, middle and bottom) compared to the basic AP heat sink, thus demonstrating clearly how the composite material was indeed providing improved heat distribution away from the heated surface.
Similarly, improved heat transfer properties are also the subject of interest in the design of polymer ‘heat pipes’, as they are considered as flexible systems for effective thermal control of various heat loaded devices.51 Therefore, to demonstrate the potential of the printable composite material for application in polymer heat pipes, a 3D coiled cooling system was designed and printed, consisting of a rectangular bar (l = 30 mm, w = 30 mm, h = 25 mm) with a 3 mm hollow internal coil, in both the AP resin and the APD-30 composite material (Fig. 8a and b). Hot water at 40 °C was continuously pumped at constant speed through the coil and once again IR thermal imaging used to capture the heat distribution within the printed blocks. The IR images of the AP cooling system showed that water cooled relatively little as it passed through the coil, with the temperature of water dropping from 39 °C to 30 °C (Fig. 8c) before it leaves the system. However, the water passing through the APD composite coil was cooled far more efficiently. IR images of the APD-30 composite coil showed a decrease in temperature of the water from 39 °C to 25 °C (room temperature) (Fig. 8d) before exiting the system. These results again demonstrate the superior heat transfer abilities of the APD-30 composite materials compared to the original polymeric material.
This work has established new possibilities in the rapid fabrication of composite materials using stereolithographic 3D printers. This work can be taken to the next level by developing similar polymer composite with alternative functional fillers e.g. magnetic particles and electrically conducting particles for a vast range of applications.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra05261d |
This journal is © The Royal Society of Chemistry 2016 |