Subscriber access provided by UNIV OF NEBRASKA - LINCOLN

Article
Multifunctional Stiff Carbon Foam Derived from Bread
Ye Yuan, Yujie Ding, Chunhui Wang, Fan Xu, Zaishan Lin, Yuyang
Qin, Ying Li, Minglong Yang, Xiaodong He, Qingyu Peng, and Yibin Li
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b03985 • Publication Date (Web): 13 Jun 2016
Downloaded from http://pubs.acs.org on June 14, 2016

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Applied Materials & Interfaces is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 34 ACS Applied Materials & Interfaces

1
2
3
4 Multifunctional Stiff Carbon Foam Derived from Bread
5
6
7
Ye Yuan,1 Yujie Ding,1 Chunhui Wang,1 Fan Xu,1 Zaishan Lin,1 Yuyang Qin,1Ying Li,1
8
Minglong Yang,1 Xiaodong He,1 Qingyu Peng1,2*, Yibin Li1,*
9
10 1
11 Center for Composite Materials and Structures, Harbin Institute of Technology,
12 Harbin 150080, P. R. China
13 2
14 Division of Aircraft Dynamics and Control, School of Astronautics, Harbin Institute
15 of Technology, Harbin 150080, P. R. China
16
17
18 ABSTRACT
19
20 The creation of stiff yet multifunctional three dimensional porous carbon
21
22
23 architecture at very low cost is still challenging so far. In this work, lightweight and
24
25 stiff carbon foam (CF) with adjustable pore structure was prepared by using flour as
26
27
28 basic element via a simple fermentation and carbonization process. The compressive
29
30 strength of CF exhibits a high value of 3.6 MPa while its density is 0.29 g/cm3
31
32
33 (compressive modulus can be 121 MPa). The electromagnetic interference (EMI)
34
35 shielding effectiveness measurements (specific EMI shielding effectiveness can be
36
37
38 78.18 dB·cm3·g-1) indicate that CF can be used as lightweight, effective shielding
39
40 material. Unlike ordinary foam structure materials, the low thermal conductivity
41
42
43 (lowest is 0.06 W/m·K) with high resistance to fire makes CF a good candidate for
44
45 commercial thermal insulation material. These results demonstrate a promising
46
47
48 method to fabricate an economical, robust carbon material for applications in industry
49
50 as well as topics regarding environmental protection and improvement of energy
51
52
53 efficiency.
54
55
56 KEYWORDS: Carbon foam, tunable pore structure, mechanically stiff, EMI
57
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 2 of 34

1
2
3
4 shielding, thermal insulating
5
6
7 INTRODUCTION
8
9 Carbon foams have an interconnected three-dimensional cellular network, which
10
11
12 endows them with many attractive performances including lightweight, adjustable
13
14 thermal and electrical conductivity, high temperature tolerance and impact damping
15
16
17 properties. Therefore, carbon foams have been widely used in various applications
18
19
such as thermal management, aerospace, energy storage and damping absorption1-8.
20
21
22 Creating foam structures using bottom-up approach allow tailoring of properties by
23
24
integrating specific elements in suitable proportions. Although graphene sheets have
25
26
27 been attracted tremendous interests and have been widely used in making monolithic
28
29
foams,1, 9-14 the prepared foams are associated with conspicuous problems of poor
30
31
32 mechanical stability. Further, fabrication graphene foams requires various complex
33
34
35
operations, long time, and relatively high costs, making largescale production of
36
37 graphene foams quite difficult. Thus, developing an environmentally friendly and
38
39
40
inexpensive approach to fabricate mechanically stiff foams is still a great scientific
41
42 and engineering challenge unresolved.
43
44
45 Biomass is a qualified carbon raw material for the preparation of valuable carbon
46
47 materials because it is available in high quality and huge amount, and is an
48
49
50 environmentally friendly renewable resource. Recently, carbon foams based on
51
52 biomass (such as watermelon,15, 16 lignin,17 bagasse,18 pomelo peel,19 banana peel,20
53
54
55 bacterial fiber,21, 22 bacterial cellulose23, 24 et al) have been successfully fabricated by
56
57 different methods, including freeze-drying,25 hydrothermal treatment,26 ionothermal
58
59
60
ACS Paragon Plus Environment
Page 3 of 34 ACS Applied Materials & Interfaces

1
2
3
4 carbonization (ITC),27 and direct carbonization.28, 29
Among these methods, direct
5
6 carbonization is the most commonly used and low-cost route. As a sustainable
7
8
9 material, biomass can be directly transformed into carbon foam under proper
10
11 carbonization conditions. These carbon materials have shown great potential in fields
12
13
14 such as energy storage, oil absorption, drug delivery and catalysis. For instance, Wu et
15
16 al.30 fabricated ultralight and flexible carbon nanofiber aerogels from bacterial
17
18
19 cellulose by pyrolysis at a high temperature, which shows high oil absorption
20
21 performance and fire resistance. However, for biomass derived foam structure
22
23
24 material, uncontrollable inner pore structures have a huge impact on its mechanical
25
26 stability, thermal or electromagnetic performance. What’ s more, the inherent limits
27
28
29 on diversity of raw materials, together with the lack of structural control of inner pore
30
31 morphology, present main challenges in fabricating tunable pore structure foams.
32
33
34 These features would seriously restrict biomass derived foam materials into actual
35
36 engineering applications.
37
38
39 Herein，a low-cost, green and template-free carbonization method was adopted
40
41
to form a tunable hierarchical morphology carbon foam with good mechanical
42
43
44 stability, high EMI shielding efficiency and thermal property. Different from previous
45
46
reports on carbon foams or hierarchical porous structures, 31 our carbon foam is a
47
48
49 self-assembled structure that uses flour as basic element and inherits the shape and
50
51
original hierarchical network structure from the bread. The carbon foam is
52
53
54 mechanically stiff and able to sustain a considerable load without deformation. We
55
56
57
demonstrated potential applications of the carbon foams as high performance
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 4 of 34

1
2
3
4 electromagnetic interference shielding and thermal insulating porous carbon materials
5
6 with high fire resistance.
7
8
9 EXPERIMENTAL SECTION
10
11 Materials. The flour and yeast were purchased from local supermarket. All water
12
13
14 used to dissolve dry yeast and mix with flour is deionized (DI) water (18.2 MΩ,
15
16 Milli-Q, Millipore Co.).
17
18
19 Preparation of Carbon Foam. In a typical process, 5g dry yeast was dissolved in
20
21 115mL water by stirring. After completely dissolved, the mixture was poured into
22
23
24 300g flour, which was placed in a dough mixer in advance. The dough mixer kneaded
25
26 slowly for about 10 minutes until wet flour cohered to a paste. The paste fermented
27
28
29 for about 60 minutes at 35℃ to form the porous structures. Then, the bread was
30
31 baked in an oven at 180℃ for 40 minutes. After that, the bread was sent into an oven
32
33
34 to dry for 18 hours at 80℃. Finally, the dry bread was put into a laboratory tube
35
36 furnace under Argon gas conditions to carbonize at different temperature. Heating rate
37
38
39 was set as 10 ℃/min and the holding time was set as 120 min. Lastly, the sample was
40
41
natural cooled in Ar atmosphere till room temperature.
42
43
44 Materials Characterization. The surface morphology of carbon foam was
45
46
characterized by field-emission scanning electron microscope (FESEM) (Carel Zeiss,
47
48
49 supra55), whereas transmission electron microscopy (TEM) images were acquired on
50
51
a TecnaiG220 transmission electron microscope operating at 160 kV. Fourier
52
53
54 transform infrared (FT-IR) spectroscopy was obtained with a TENSOR 27 from
55
56
57
Bruker. X-ray powder diffraction was conducted using a Philips X' Pert PRO
58
59
60
ACS Paragon Plus Environment
Page 5 of 34 ACS Applied Materials & Interfaces

1
2
3
4 diffractometer with nickel-filtered Cu Kα radiation. Raman spectra were obtained
5
6 with a Lab RAM HR800 from JY Horiba. The nitrogen sorptions of samples were
7
8
9 measured at Autosorb iQ from Quantachrome Instruments. The apparent surface area
10
11 was calculated using the BET method, at 77 K. The pore size distribution plots were
12
13
14 recorded from the desorption branch of the isotherms based on the
15
16 Barrett-Joyner-Halenda (BJH) model. The carbon (C), nitrogen (N) and oxygen (O)
17
18
19 contents of materials were analyzed using an X-ray photoelectron spectroscopy (XPS)
20
21 (VG Scientific ESCALAB Mark Ⅱspectrometer). Element analysis of samples was
22
23
24 also measured by EDS, Oxford Instrument.
25
26 Thermal and EMI Performance Test. The thermal conductivity was tested using
27
28
29 TPS 2500S from Hot Disk at room temperature. The tested samples were prepared by
30
31 cutting into cylinder with R=30 mm, h =10 mm. The electrical conductivity was tested
32
33
34 using PARSTAT 4000, Princeton Applied Research. The sample was cut into 30
35
36 mm×5 mm ×5 mm strips. Two silver wires were stuck to both small area side of the
37
38
39 strip by elargol to connect the instrument for test. Transmission coefficient S and
40
41
electromagnetic interference shielding were measured by Vector Network Analyzer
42
43
44 (Agilent TechnologiesN5227A, USA). Wax was used as binder and matrix material
45
46
for preparing samples. Two kinds of wax composites samples with different carbon
47
48
49 foam content (10% and 30%) were prepared to make a comparison of dielectric
50
51
properties.
52
53
54
55 RESULTS AND DISCUSSION
56
57 Formation of Tunable Pore Structure Carbon Foam. We prepared carbon foam
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 6 of 34

1
2
3
4 with various densities (0.08 ~ 0.3 g/cm3) simply by adjusting the concentrations of
5
6 starting materials. The unique advantages of the hierarchical pore structure can be
7
8
9 further demonstrated by following performance test. The preliminary fabrication step
10
11 is based on bread making process, subsequent carbonization sketch is illustrated in
12
13
14 Figure 1, in which flour-based (containing glucose and protein) bread was used as a
15
16 carbon source. After simply carbonized in Argon gas atmosphere, the dry bread was
17
18
19 transformed into carbon foam. The original shape of pore structure remains but their
20
21 size reduces compared with dry bread. This process comprised of two reactions,
22
23
24 involving dehydration and carbonization. During carbonizing in Argon gas
25
26 atmosphere, the following reaction would take place:
27
28
29 (C6H10O5)n (starch)→6n C+5n H2O (1)
30
31 Pore size and distribution are important factors determining the properties of
32
33
34 porous carbon materials.32 Carbon foams with larger and irregular pores usually have
35
36 a low density. The hierarchical pore structures can be tuned by many factors. In this
37
38
39 work, two extremely important factors, yeast and water content, were investigated to
40
41
realize the control of hierarchical morphology during fermentation process.
42
43
44 The assumed evolution of pore growth process during fermentation was shown in
45
46
Figure 2a. The left SEM image in Fig 2b shows carbon foam fabricated with dry yeast
47
48
49 content of 0.5 g per 100 g flour (where 55ml water was added per 100 g flour).
50
51
Near-round pores a few hundred of micrometers in size can be visible to the naked
52
53
54 eye. On closer inspection, a mass of round pores concentratively distribute in the cell
55
56
57
walls between two large neighboring pores. The size of these smaller pores ranges
58
59
60
ACS Paragon Plus Environment
Page 7 of 34 ACS Applied Materials & Interfaces

1
2
3
4 from few to several ten microns. A high magnification image is shown in Figure 2d, it
5
6 can be observed that some of these pores are open structure, but some are covered
7
8
9 with transparent hemisphere carbon film. The TEM image of the foam is also shown
10
11 in Figure 2d. A series of oval pore with size in hundred nanometers can be observed.
12
13
14 These nano-pores may come from the remove of impurity during carbonization. The
15
16 above images reveal a hierarchical pore structure ranges from millimeter to nanometer
17
18
19 scale. The middle SEM image in Figure 2b shows carbon foam fabricated with dry
20
21 yeast content of 1.0 g per 100 g flour. Obviously, pores turn to be irregular, and many
22
23
24 small pores randomly distribute in the cell walls. On further increasing the dry yeast
25
26 to 1.5 g per 100 g flour, carbon foam with larger and disordered pore structure can be
27
28
29 obtained. Also, quantities of minor pores in cell walls increased. The diameter of large
30
31 pores can be as large as 2~3 millimeter.
32
33
34 Figure 2c shows the cross section morphologies of carbon foam containing with
35
36 different water content (the yeast content keeps 1.0 g per 100 g flour). Familiar with
37
38
39 changing yeast content, the pores tend to be larger and irregular while adding more
40
41
water. On the contrary, quantities of minor pores in the cell walls do not increase
42
43
44 synchronously. Instead, these pores tend to become larger and irregular. We also
45
46
characterize the specific surface area by BET analyzer. The maximum BET specific
47
48
49 surface area of obtained carbon foam measured is 988 m2/g (for large and irregular
50
51
pore structure), and the minimum value is only 19 m2/g (for round and regular pore
52
53
54 structure), as shown in Figure 3f. Pore distributions measured by BET analyzer are
55
56
57
illustrated in the inset picture in Figure 3f. It can be observed that pores with a
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 8 of 34

1
2
3
4 diameter of 3 nm and 5 nm domain in the micro-pore range, which shows the same
5
6 trend in both of these two materials.
7
8
9 Above all, by changing the content of yeast and water, inner pore structure and
10
11 morphology can be simply tuned without any template. We further analyzed the pore
12
13
14 growth process in the bread. Yeast and water provide a vital role during formation of
15
16 pore structure. After adding water, the starches can be gelatinized and proteins in the
17
18
19 flour fully absorb water to form a gluten network structure. Meanwhile, the yeast will
20
21 produce and release carbon dioxide gases to form pores when dispersing in the paste.
22
23
24 According to the balance of pressure, the process of pore growth would be
25
26 affected by hydrostatic pressure and additional surface pressure of the paste, which
27
28
29 can be expressed as:
30
31 Pc= Pstat +Psurf (2)
32
33
34 where Pc is the pressure that the released gases can be afforded. Pstat is the sum of
35
36 atmospheric pressure and whole hydrostatic pressure. Psurf relates to surface tension
37
38
39 and gluten network of pores.
40
41
It is obvious that the pore morphology is closely associated with the gas pressure
42
43
44 and strength of gluten network. Gas pressure mainly depends on the amount of gas
45
46
produced from yeast, and strength of gluten network is closely related to the
47
48
49 proportion of water adding into flour. When adding more yeast in the paste, both gas
50
51
amounts and active site will increase. At the same time, the strength of gluten network
52
53
54 will decrease after adding excess water. Finally, pore structure was determined under
55
56
57
the balance of above two factors. It is worth noting that the pore shape and size would
58
59
60
ACS Paragon Plus Environment
Page 9 of 34 ACS Applied Materials & Interfaces

1
2
3
4 be out of control once excessive amounts of yeast and water added in the paste.
5
6 The composition of carbon foam was analyzed by XPS, XRD pattern, Raman
7
8
9 spectroscopy and FT-IR spectroscopy. X-ray photoelectron spectroscopy (XPS)
10
11 analysis in Figure 3a reveals changes in the nitrogen N 1s band for samples
12
13
14 carbonized at 500ºC and 2000ºC. The content of nitrogen was estimated to be 2.95%
15
16 carbonized at 500 ℃, but this value decreased to 0% when carbonized at 2000 ℃.
17
18
19 Also, the content of oxygen decreased from 8.87% to 4.41%. This indicates the
20
21 removal process of organics when increasing the carbonized temperature. The C1s
22
23
24 spectrum ranging from 280.5 to 289 eV is shown in Figure 3b. After carefully being
25
26 fitted toward C1s, it can be divided into three obvious peaks centering at ca. 284.58,
27
28
29 285.48 and 286.18 eV. For B500, the binding energy at ca. 284.5 eV can be attributed
30
31 to sp2 C–sp2 C bonds, ca. 285.48 eV corresponding to sp3-C bonds, while ca. 286.49
32
33
34 eV assignable to C–O bonds. Figure 3c shows powder X-ray diffraction (XRD) in the
35
36 wide-angle region of the carbon foam. Peak at 22.3º and a weak peak at 43.8º can be
37
38
39 attributed to typical reflections from the (002) and (100) planes of disordered carbon
40
41
materials. These weak diffraction peaks indicate that no graphitization occurred under
42
43
44 the present carbonization process. [33]
45
46
Raman spectroscopy is a powerful analytical tool for quantifying the properties of
47
48
49 carbon materials. Two major Raman signals can be indented, as shown in Figure 3d.
50
51
The peaks located at around 1320 and 1590 cm-1 are assigned to the characteristic D
52
53
54 (defects and disorder) and G (graphitic) bands of carbon materials, respectively. The
55
56
57
D/G ratio of band intensities indicates the degree of structural order with respect to a
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 10 of 34

1
2
3
4 perfect graphitic structure. Here, the D/G intensity ratios of B500, B1000, B1500 and
5
6 B2000 were determined to be 1.12, 0.99, 0.91 and 0.69 respectively. The relatively
7
8
9 lower D/G intensity ratio for B2000 might indicate a reduced amount of heteroatom
10
11 doping (such as N and O). The high temperature is revealed to be a key factor in
12
13
14 obtaining a high degree of carbonization with few defects in the carbon structure.
15
16 Fourier transform infrared (FT-IR) spectroscopy was used to identify the surface
17
18
19 functional groups of samples, as shown in Figure 3(e). The band at 3420 cm-1 is
20
21 attributed to the O-H stretching vibrations. The observed bands at 1629 cm-1 are
22
23
24 attributed to the C=C stretching vibrations. The bands at about 1450 ~ 1380 cm-1 can
25
26 be attributed to C-H bending vibration. The bands at 1100 and 880 cm-1 can be
27
28
29 ascribed to the C-O-C stretching vibration and deformation vibration of vinyl C-H,
30
31 respectively[15].The apparent change of C-H vibration band at 1450 ~ 1380 cm−1 in
32
33
34 Figure 3e suggests micro structure changes of carbon foam at different carbonized
35
36 temperature.
37
38
39 Mechanical Strength Figure 4a shows the compressive strength of CF carbonized
40
41
at 1000 ℃ with different bulk density. It is observed that the compressive strength
42
43
44 strongly depends on its bulk density. The insert simplified pore structure evolution
45
46
indicates the effect of density to the pore structure. The maximum compressive
47
48
49 strength of tested carbon foam is about 3.6 MPa with a low density of 0.29 g/cm3 and
50
51
its compressive modulus can be about 121 MPa, which is higher than the values for
52
53
54 previously reported carbon foams with the same density. This relatively high strength
55
56
57
and modulus is related to the high moduli of carbon particle, and the fact that the
58
59
60
ACS Paragon Plus Environment
Page 11 of 34 ACS Applied Materials & Interfaces

1
2
3
4 carbon particle makes the cell walls stiffer by crosslinking. Also, micro and macro
5
6 structure plays a significantly important role in its mechanical property.1 What’s more,
7
8
9 the unique interconnected 3D network structure attributes to the strong mechanical
10
11 properties, suggesting that the CF have a great potential for robust 3D functional
12
13
14 materials. Actually, the compressive strength and modulus may have a little difference
15
16 for samples with almost the same density. This mainly attributes to the tiny difference
17
18
19 of microstructure, which cannot be controlled so precisely by our method. In order to
20
21 obtain a more reliable result, number of tested samples with the same carbonized
22
23
24 temperature or same density was at least three. Finally, the obtained result is the mean
25
26 values of tested results. Also, error bars were added according to standard deviation
27
28
29 calculation. In order to explain the effect of pore structure on mechanical performance,
30
31 a finite element method (FEM) was employed to analyze the stress distribution in a
32
33
34 2D cross section just prior to its sudden collapse. The affecting variables to
35
36 compressive strength, such as porosity, pore shape and distribution, are briefly
37
38
39 discussed in Supporting Information Figure S7. Figure S7c, e and g are the simplified
40
41
simulation geometry for compression analysis that own larger porosity, different pore
42
43
44 shape and disordered pore distribution compared with Figure S7a. Figure S7d, f and h
45
46
are the maps of Mises stress on the x-y plane of the carbon foam. When applied with
47
48
49 equal compressive stress from top of the block, it can be clearly seen that the
50
51
maximum stress on the pore edge node in Figure S7a, is much smaller than that in
52
53
54 Figure S7d, f and h. It means for carbon foam with larger porosity, irregular pore size
55
56
57
and disordered pore distribution, they are easy to cause cracks under the same
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 12 of 34

1
2
3
4 mechanical compression. The trend of FEM analysis is in line with our experimental
5
6 results. Figure 4b shows the corresponding compressive modulus of CF (all of the
7
8
9 bulk densities range from 0.21 to 0.22 g/cm3) carbonized from 500 ℃ to 2000 ℃. It
10
11 can be observed that the carbon foam carbonized at 1000 ℃ obtained the largest
12
13
14 modulus. The compressive modulus of samples increased from 62.64 MPa to 121
15
16 MPa, when carbonized temperature rose from 500 ℃ to 1000 ℃. But, after that,
17
18
19 modulus decreased when carbonized at higher temperature. For example, when the
20
21 carbonized temperature reaches 2000℃, the modulus was down to 57.73 MPa. It can
22
23
24 be concluded that 1000 ℃ is the best carbonized temperature if a stiff foam is
25
26 required.
27
28
29 The comparison of load state between real bread and carbon foam is shown in
30
31 Figure 4c. It can be observed that the bread was squashed after a 100 g weight
32
33
34 standing on it. Contrarily, the carbon foam is stiff enough to carry the same weight
35
36 without deformation. The carbon foam can also stand on a bamboo leaf, which shows
37
38
39 its light weight.
40
41
EMI Shielding Efficiency Electromagnetic interference (EMI) shielding is
42
43
44 currently in high demand for both commercial and defense purposes.11, 34-38

45
46
Conventional EMI shielding materials are usually heavy or unable to sustain a
47
48
49 considerable load, especially in spaceship and aircraft. Thus, the CF provides a
50
51
competitive candidate for the application in aerospace engineering. Figure 5a and b
52
53
54 shows the electromagnetic parameters of wax composites, containing weight of 30%
55
56
57
and 10% carbon foam (carbonized at 1000℃). As shown in Figure 5a, the ε′ and ε″
58
59
60
ACS Paragon Plus Environment
Page 13 of 34 ACS Applied Materials & Interfaces

1
2
3
4 values of ε′10% and ε″10% tend to keep steady at 3.30 and 0 with increasing frequency.
5
6 However, the ε′ values of ε′30% decreases continuously from 11.51 to 8.72 until at 14.9
7
8
9 GHz and then increases to 9.53. The opposite situation occurs at the value of ε″30%,
10
11 the ε″ values of ε″30% increases at first and then gradually decreases from its peak at
12
13
14 4.23 at 12.00 GHz to 2.16 at 18 GHz, with increasing frequency. It is also clearly
15
16 observed that the value of ε′30% and are ε″30% significantly larger than those of ε′10%
17
18
19 and are ε″10%. Likewise, tan δE of C30% is greater than that of C10% (Figure 5b). This
20
21 indicates that C30%, as compared to C10%, exhibits higher storage and loss capabilities
22
23
24 for electric energy. Permittivity behavior mainly attributes to the increase of electric
25
26 conductivity. Usually, the permittivity values of carbon/resin composites increase with
27
28
29 increasing loading of carbon particles, which is called percolation theory.
30
31 The EMI shielding effectiveness of a material is defined as the ratio between the
32
33
34 incoming power (Pin) and outgoing power (Pout) of an electromagnetic wave. In
35
36 general, SE is expressed in decibels (dB). In this study, the EMI shielding
37
38
39 effectiveness of CF was measured using an Agilent N5234A vector network analyzer.
40
41
An electromagnetic wave was injected directly into the foam using a waveguide setup.
42
43
44 Details on the EMI shielding effectiveness measurement of CF are provided in the
45
46
Supporting Information. The measured CF was carbonized at 1000℃ with an electric
47
48
49 conductivity of 0.26 S/cm. Because of the limit of the measurement equipment, we
50
51
only analyzed the effectiveness scanned from 6.0 to 12.4 GHz range. It is observed in
52
53
54 Figure 5d that the shielding effectiveness of CF is almost independent of the
55
56
57
frequency in the measured frequency region. The shielding effectiveness of CF with
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 14 of 34

1
2
3
4 thickness 3 mm is measured to be about 15.7 dB over a frequency range of 6.0-12.4
5
6 GHz. This increment of the EMI shielding effectiveness is attributed mainly to the
7
8
9 interconnected hierarchical carbon pore networks. The increased pores could attenuate
10
11 the incident electromagnetic microwaves by reflecting and scattering between cell
12
13
14 walls, and the microwaves were hard to escape from the CF before being absorbed
15
16 and transferred to heat, as is shown in Figure 5c. The results also show that the EMI
17
18
19 shielding effectiveness increases with increasing CF thickness. The EMI shielding
20
21 effectiveness for CF with thickness of 4 mm and 5 mm is about 16.3 dB and 17.2 dB.
22
23
24 For aircraft or aerospace applications, density has to be taken into consideration. The
25
26 specific EMI shielding effectiveness (EMI shielding effectiveness divided by the
27
28
29 density) is more appropriate for use in comparing the shielding performance between
30
31 typical metals and CF. In this work, the specific EMI shielding effectiveness of
32
33
34 measured CF (thickness is 3 mm) is calculated to be 71.36 dB·cm3·g-1, which is much
35
36 higher than that of shielding metals (compared to 10 dB·cm3·g-1 for solid copper).
37
38
39 We further analyzed the EMI shielding mechanism of CF. When an
40
41
electromagnetic wave is incident on a shielding material, the incident power is
42
43
44 divided into reflected power, absorbed power and transmitted power. The total EMI
45
46
shielding effectiveness (SE) is the sum of the effectiveness of all attenuating
47
48
49 mechanisms, including absorption (LA), reflection (LR), and can be expressed in the
50
51
following equation: SE = 20log(1/|S12|)= LA (dB)+LR (dB), where LA=(1-|S11|2)/(|S12|2),
52
53
54 and LR=1/(1-|S11|2). Figure 5e displays the electrical conductivity of CF as a function
55
56
57
of carbonized temperature measured at room temperature. It can be seen that, the
58
59
60
ACS Paragon Plus Environment
Page 15 of 34 ACS Applied Materials & Interfaces

1
2
3
4 conductivity sharply increases when increase the carbonized temperature from 500℃
5
6 (σ500= 1.94 × 10-8 S/cm) to 1000 ℃ (σ1000=0.263 S/cm). After enhancing the
7
8
9 carbonized temperature to 1500℃ or 2000℃, the conductivity has a less increase.
10
11 Figure 5f shows SE, LA and LR of CF as a function of electrical conductivity at the
12
13
14 frequency of 9 GHz. Obviously, SE, LA and LR increase with increasing electrical
15
16 conductivity. What’s more, the contribution of LA to the EMI shielding effectiveness
17
18
19 is much larger than that of LR. It is observed that CF with a conductivity of 0.357
20
21 S/cm, SE, LA and LR are 18.37 dB, 3.40 dB and 16.97 dB, respectively. Through the
22
23
24 above results, it is suggested that contributes more to the EMI SE of CF in this
25
26 frequency region. This mainly attributes to the hierarchical pores which increase the
27
28
29 reflection and scattering of microwave in the body of CF. The introduction of pores in
30
31 CF body not only decreases its density but also increases the EMI efficiency.
32
33
34 Thermal Performance Thermal insulation plays a major role in controlling the
35
36 energy efficiency. Commercial organic thermal insulating materials often show poor
37
38
39 fire resistance, along with toxicity problems. Therefore, developing new inorganic
40
41
thermal insulating materials with high security to substitute for original flammable
42
43
44 organic thermal insulation materials is significantly important. Figure 6a shows the
45
46
thermal conductivity of carbon foam (bulk density ranges from 0.17~0.18 g/cm3)
47
48
49 derived from different carbonization temperature. It is observed that the thermal
50
51
52
conductivity of CF carbonized at 500℃ is as low as 0.06 W/m·K. When raising
53
54 carbonized temperature to 2000℃, the thermal conductivity increased to 0.28 W/m·K.
55
56
57
Actually, thermal conductivity of samples with the same treated condition has a tiny
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 16 of 34

1
2
3
4 difference. This is mainly attributed to the control of inner pore morphology of porous
5
6 materials cannot be as precise as ensuring each sample the same. Thus, we prepared
7
8
9 the measured samples as the same way with mechanical performance test. The
10
11 thermal conductivity of each sample was measured for four times. Number of tested
12
13
14 samples with the same carbonized temperature or same density was at least three.
15
16 Finally, the obtained thermal conductivity is the mean values of tested results. Also,
17
18
19 error bars were added according to standard deviation calculation. The low thermal
20
21 conductivity of carbon foam can be related to the thermal properties of nano-sized
22
23
24 components and the microstructure in the cell wall. Heat conduction in carbon
25
26 materials is usually dominated by phonons, which can be explained by strong sp2
27
28
29 bonding resulting in efficient heat transfer by lattice vibrations.39, 40 When carbonizing
30
31 at 500℃, the organics existed in the bread cannot be removed clearly. Also, the CF
32
33
34 has a lower degree of intralayer condensation and disordered micro carbon structure
35
36 with many defects. Those defects and impurity may reduce mean free path of phonon
37
38
39 and impart an interfacial thermal resistance which reduce the conductivity.35 After
40
41
raising the carbonizing temperature, the CF base would remain fewer and fewer
42
43
44 impurity. At the same time, the micro carbon structure turns to be aligned with each
45
46
other, which has been proved in above XPS and XRD analysis. Thus, less defects and
47
48
49 rough edges in the sample contribute a high heat transfer. In order to investigate the
50
51
effect of microstructure to heat transfer, thermal conductivity of carbon foam with
52
53
54 different bulk densities (e.g. carbonized at 1000 ℃) was measured. Figure 6b shows
55
56
57
the bulk density changes from 0.09 to 0.23 g/cm3 while thermal conductivity varying
58
59
60
ACS Paragon Plus Environment
Page 17 of 34 ACS Applied Materials & Interfaces

1
2
3
4 from 0.08 to 0.17 W/m·K. Actually, thermal conductivity will increase for higher
5
6 density samples. The relationship between thermal conductivity and porosity can be
7
8
9 estimated according to
10
11 K = (1-kε) K0 (3)
12
13
14 K is the thermal conductivity; K0 is the thermal conductivity when porosity is zero.
15
16 k is the correction factor and ε is the actual porosity.
17
18
19 For CF samples, bulk density is related to its porosity. Figure 6c illustrates the
20
21 contribution of conduction, convection and radiation to thermal conductivity of
22
23
24 carbon foam. Conduction includes solid conduction and gas conduction, and it is
25
26 known that thermal conductivity of gas is much smaller than solid. Thus, the
27
28
29 hierarchical pores shown in Figure 6c will all significantly contribute to thermal
30
31 resistance.
32
33
34 In order to show the contribution of hierarchical structure to the thermal resistance,
35
36 one-dimensional temperature distribution models were analyzed by finite element
37
38
39 method (FEM) in Figure S8. Figure S8a and b represent two hypothetically ideal
40
41
structures, large round pores and hierarchical pores. Temperature field of 300 ℃ and
42
43
44 25 ℃ is applied at the top and bottom boundaries of two models, respectively. After
45
46
a steady state heat transfer process, the temperature distributions are shown in Figure
47
48
49 S8. It is clearly observed that heat transfers slower at hierarchical pore structure than
50
51
common single pore structure under the same condition.
52
53
54 Further FEM thermal analysis on CF with different bulk density is shown in
55
56
57
Figure S9. According to the experimental observation, irregular hierarchical pore
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 18 of 34

1
2
3
4 structure (IHPS) represents low density microstructure，and therefore porosity of
5
6 IHPS is designed to be larger than that of uniform hierarchical pore structure (UHPS).
7
8
9 Temperature field of 300 ℃ and 25 ℃ is applied at the top and bottom boundaries
10
11 in Figure S9, respectively. After a steady state heat transfer process, the temperature
12
13
14 distribution for UHPS and IHPS are shown in Figure S9c and 9d. Obviously, heat
15
16 transfers faster at UHPS than that of IHPS under the same condition. The FEM
17
18
19 analysis is consistent with our experimental results. Additionally, thermal
20
21 conductivities of carbon foams keep a relatively low value. A challenge for general
22
23
24 thermal insulating materials is their poor resistance to fire. The burning experiment in
25
26 Figure 6d indicates our carbon foam has a high fire-resistance performance. These
27
28
29 results show that the carbon foam is a good candidate for thermal insulation materials.
30
31
32 CONCLUSIONS
33
34
35 We present a facile and green strategy for fabrication of lightweight yet stiff carbon
36
37
38 foam with tunable pore structure. Key factors for making tunable pore structure
39
40 carbon foam include control of yeast and water content. The carbon foam exhibited
41
42
43 low thermal conductivity, favorable EMI shielding efficiency with high compressive
44
45 modulus. Finally, this fabrication scheme could be broadly applied to other composite
46
47
48 material structures for the myriad of technologies that require lightweight, low
49
50 thermal conductivity, and high EMI shielding efficiency materials.
51
52
53
54
ASSOCIATED CONTENT
55
56 Supporting Information
57
58
59
60
ACS Paragon Plus Environment
Page 19 of 34 ACS Applied Materials & Interfaces

1
2
3
4 Carbon yields at different carbonized temperature, EDS elemental analysis of samples
5
6 carbonized at different temperature, EMI shielding measurement process, schematic
7
8
9 of thermal transport measurement, finite element method for brief mechanical and
10
11 thermal analysis, and the tested data statistic. This material is available free of charge
12
13
14 via the Internet at http://pubs.acs.org.
15
16
17 AUTHOR INFORMATION
18
19
20 Corresponding Author
21
22 *E-mail: liyibin@hit.edu.cn, Tel & Fax: +86-451-86402326
23
24
*E-mail: pengqingyu@hit.edu.cn, Tel & Fax: +86-451-86402326
25
26 Author Contributions
27
28
29 All authors have given approval to the final version of the manuscript.
30
31 Notes
32
33
34 The authors declare no competing financial interest.
35
36
37
ACKNOWLEDGMENTS
38
39 This work was supported by the Natural Science Foundation in China (NSFC
40
41
11272109, 51503052), the Ph. D. Programs Foundation of Ministry of Education of
42
43
44 China (20122302110065), the Fundamental Research Funds for the Central
45
46
Universities (Grant No. HIT. BRETIII.201507) and China Postdoctoral Science
47
48
49 Foundation funded project (Grant No. 2015M580259).
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 20 of 34

1
2
3
4 REFERENCES
5
6 (1) Vinod, S.; Tiwary, C. S.; da Silva Autreto, P. A.; Taha-Tijerina, J.; Ozden, S.;
7
8
9 Chipara, A. C.; Vajtai, R.; Galvao, D. S.; Narayanan, T. N.; Ajayan, P. M. Low-density
10
11 Three-dimensional Foam Using Self-reinforced Hybrid Two-dimensional Atomic
12
13
14 Layers. Nat. Commun 2014, 5,4541
15
16 (2) Xu, Y.; Sheng, K.; Li, C.; Shi, G. Self-Assembled Graphene Hydrogel via a
17
18
19 One-Step Hydrothermal Process. ACS Nano 2010, 4, 4324-4330.
20
21 (3) Yan, Z.; Ma, L.; Zhu, Y.; Lahiri, I.; Hahm, M. G.; Liu, Z.; Yang, S.; Xiang, C.;
22
23
24 Lu, W.; Peng, Z.; Sun, Z.; Kittrell, C.; Lou, J.; Choi, W.; Ajayan, P. M.; Tour, J. M.
25
26 Three-Dimensional Metal-Graphene-Nanotube Multifunctional Hybrid Materials.
27
28
29 ACS Nano 2013, 7, 58-64.
30
31 (4) Sudeep, P. M.; Narayanan, T. N.; Ganesan, A.; Shaijumon, M. M.; Yang, H.;
32
33
34 Ozden, S.; Patra, P. K.; Pasquali, M.; Vajtai, R.; Ganguli, S.; Roy, A. K.;
35
36 Anantharaman, M. R.; Ajayan, P. M. Covalently Interconnected Three-Dimensional
37
38
39 Graphene Oxide Solids. ACS Nano 2013, 7, 7034-7040.
40
41
(5) Geim, A. K.; Novoselov, K. S. The Rise of Graphene. Nat. Mater 2007, 6,
42
43
44 183-191.
45
46
(6) Chen, Z.; Ren, W.; Gao, L.; Liu, B.; Pei, S.; Cheng, H. M. Three-dimensional
47
48
49 Flexible and Conductive Interconnected Graphene Networks Grown by Chemical
50
51
Vapour Deposition. Nat. Mater 2011, 10, 424-428.
52
53
54 (7) Zhou, G.; Yin, L.C.; Wang, D. W.; Li, L.; Pei, S.; Gentle, I. R.; Li, F.; Cheng,
55
56
57
H.M. Fibrous Hybrid of Graphene and Sulfur Nanocrystals for High-Performance
58
59
60
ACS Paragon Plus Environment
Page 21 of 34 ACS Applied Materials & Interfaces

1
2
3
4 Lithium-Sulfur Batteries. ACS Nano 2013, 7, 5367-5375.
5
6 (8) You, B.; Jiang, J.; Fan, S., Three-Dimensional Hierarchically Porous All-Carbon
7
8
9 Foams for Supercapacitor. ACS Appl. Mater. Interfaces 2014, 6, 15302-15308.
10
11 (9) Hu, C.; Xue, J.; Dong, L.; Jiang, Y.; Wang, X.; Qu, L.; Dai, L. Scalable
12
13
14 Preparation of Multifunctional Fire-Retardant Ultralight Graphene Foams. ACS Nano
15
16 2016, 10, 1325-1332.
17
18
19 (10) Du, X.; Liu, H. Y.; Mai, Y. W. Ultrafast Synthesis of Multifunctional N-Doped
20
21 Graphene Foam in an Ethanol Flame. ACS Nano 2016, 10, 453-462.
22
23
24 (11) Nardecchia, S.; Carriazo, D.; Ferrer, M. L.; Gutierrez, M. C.; del Monte, F.
25
26 Three Dimensional Macroporous Architectures and Aerogels Built of Carbon
27
28
29 Nanotubes and/or Graphene: Synthesis and Applications. Chem. Soc. Rev 2013, 42,
30
31 794-830.
32
33
34 (12) Chen, Z.; Xu, C.; Ma, C.; Ren, W.; Cheng, H. M. Lightweight and Flexible
35
36 Graphene Foam Composites for High-Performance Electromagnetic Interference
37
38
39 Shielding. Adv. Mater. 2013, 25, 1296-1300.
40
41
(13) Sun, H.; Xu, Z.; Gao, C. Multifunctional, Ultra-Flyweight, Synergistically
42
43
44 Assembled Carbon Aerogels. Adv. Mater. 2013, 25, 2554-2560.
45
46
(14) Chen, W.; Li, S.; Chen, C.; Yan, L. Self-Assembly and Embedding of
47
48
49 Nanoparticles by In Situ Reduced Graphene for Preparation of a 3D
50
51
Graphene/Nanoparticle Aerogel. Adv. Mater. 2011, 23, 5679-5683.
52
53
54 (15) Wu, X. L.; Wen, T.; Guo, H. L.; Yang, S.; Wang, X.; Xu, A. W.
55
56
57
Biomass-Derived Sponge-like Carbonaceous Hydrogels and Aerogels for
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 22 of 34

1
2
3
4 Supercapacitors. ACS Nano 2013, 7, 3589-3597.
5
6 (16) Ren, Y. M.; Xu, Q.; Zhang, J. M.; Yang, H. X.; Wang, B.; Yang, D. Y.; Hu, J. H.;
7
8
9 Liu, Z. M. Functionalization of Biomass Carbonaceous Aerogels: Selective
10
11 Preparation of MnO2@CA Composites for Supercapacitors. ACS Appl. Mater.
12
13
14 Interfaces 2014, 6, 9689-9697.
15
16 (17) Yang, Y.; Tong, Z.; Ngai, T.; Wang, C. Nitrogen-Rich and Fire-Resistant Carbon
17
18
19 Aerogels for the Removal of Oil Contaminants from Water. ACS Appl. Mater.
20
21 Interfaces 2014, 6, 6351-6360.
22
23
24 (18) Hao, P.; Zhao, Z.; Tian, J.; Li, H.; Sang, Y.; Yu, G.; Cai, H.; Liu, H.; Wong, C. P.;
25
26 Umar, A. Hierarchical Porous Carbon Aerogel Derived from Bagasse for High
27
28
29 Performance Supercapacitor Electrode. Nanoscale 2014, 6, 12120-12129.
30
31 (19) Liang, Q.; Ye, L.; Huang, Z. H.; Xu, Q.; Bai, Y.; Kang, F.; Yang, Q. H. A
32
33
34 Honeycomb-like Porous Carbon Derived from Pomelo Peel for Use in
35
36 High-performance Supercapacitors. Nanoscale 2014, 6, 13831-13837.
37
38
39 (20) Liu, R. L.; Yin, F. Y.; Zhang, J. F.; Zhang, J.; Zhang, Z. Q. Intestine-like
40
41
Micro/mesoporous Carbon Built of Chemically Modified Banana Peel for
42
43
44 Size-selective Separation of Proteins. RSC Adv. 2014, 4, 21465-21470.
45
46
(21) Rojo, E.; Alonso, M. V.; Oliet, M.; Del Saz-Orozco, B.; Rodriguez, F. Effect of
47
48
49 Fiber Loading on the Properties of Treated Cellulose Fiber-reinforced Phenolic
50
51
Composites. Compos. Pt. B-Eng. 2015, 68, 185-192.
52
53
54 (22) Zhang, Z.; Sebe, G.; Rentsch, D.; Zimmermann, T.; Tingaut, P. Ultralightweight
55
56
57
and Flexible Silylated Nanocellulose Sponges for the Selective Removal of Oil from
58
59
60
ACS Paragon Plus Environment
Page 23 of 34 ACS Applied Materials & Interfaces

1
2
3
4 Water. Chem. Mater. 2014, 26, 2659-2668.
5
6 (23) Svagan, A. J.; Samir, M. A. S. A.; Berglund, L. A. Biomimetic Foams of High
7
8
9 Mechanical Performance Based on Nanostructured Cell Walls Reinforced by Native
10
11 Cellulose Nanofibrils. Adv. Mater. 2008, 20, 1263-1269.
12
13
14 (24) Wu, Z. Y.; Li, C.; Liang, H. W.; Chen, J. F.; Yu, S. H. Ultralight, Flexible, and
15
16 Fire-Resistant Carbon Nanofiber Aerogels from Bacterial Cellulose. Angew. Chem.,
17
18
19 Int. Ed. 2013, 52, 2925-2929.
20
21 (25) Ren, Y.; Zhang, J.; Xu, Q.; Chen, Z.; Yang, D.; Wang, B.; Jiang, Z.
22
23
24 Biomass-derived Three-dimensional Porous N-doped Carbonaceous Aerogel for
25
26 Efficient Supercapacitor Electrodes. RSC Adv. 2014, 4, 23412-23419.
27
28
29 (26) Sevilla, M.; Gu, W.; Falco, C.; Titirici, M. M.; Fuertes, A. B.; Yushin, G.
30
31 Hydrothermal Synthesis of Microalgae-derived Microporous Carbons for
32
33
34 Electrochemical Capacitors. J. Power Sources 2014, 267, 26-32.
35
36 (27) Zhang, P.; Gong, Y.; Wei, Z.; Wang, J.; Zhang, Z.; Li, H.; Dai, S.; Wang, Y.
37
38
39 Updating Biomass into Functional Carbon Material in Ionothermal Manner. ACS Appl.
40
41
Mater. Interfaces 2014, 6, 12515-12522.
42
43
44 (28) Tao, X. Y.; Zhang, J. T.; Xia, Y.; Huang, H.; Du, J.; Xiao, H.; Zhang, W. K.; Gan,
45
46
Y. P. Bio-inspired Fabrication of Carbon Nanotiles for High Performance Cathode of
47
48
49 Li-S Batteries. J. Mater. Chem. A 2014, 2, 2290-2296.
50
51
(29) Qian, W. J.; Sun, F. X.; Xu, Y. H.; Qiu, L. H.; Liu, C. H.; Wang, S. D.; Yan, F.
52
53
54 Human Hair-derived Carbon Flakes for Electrochemical Supercapacitors. Energy
55
56
57
Environ. Sci. 2014, 7, 379-386.
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 24 of 34

1
2
3
4 (30) Wu, Z. Y.; Li, C.; Liang, H. W.; Chen, J. F.; Yu, S. H. Ultralight, Flexible, and
5
6 Fire-Resistant Carbon Nanofiber Aerogels from Bacterial Cellulose. Angew. Chem.,
7
8
9 Int. Ed. 2013, 125, 2997-3001.
10
11 (31) Chen, B.; Zhang, S.; Zhang, Q.; Mu, Q.; Deng, L.; Chen, L.; Wei, Y.; Tao, L.;
12
13
14 Zhang, X.; Wang, K., Microorganism Inspired Hydrogels: Fermentation Capacity,
15
16 Gelation Process and Pore-forming Mechanism Under Temperature Stimulus. RSC
17
18
19 Adv. 2015, 5, 91937-91945.
20
21 (32) Barg, S.; Perez, F. M.; Ni, N.; do Vale Pereira, P.; Maher, R. C.;
22
23
24 Garcia-Tuñon, E.; Eslava, S.; Agnoli, S.; Mattevi, C.; Saiz, E., Mesoscale Assembly
25
26 of Chemically Modified Graphene into Complex Cellular Networks. Nat. Commun
27
28
29 2014, 5,4328
30
31 (33) Pradhan, B. K.; Sandle, N. K., Effect of Different Oxidizing Agent Treatments
32
33
34 on the Surface Properties of Activated Carbons. Carbon 1999, 37, 1323-1332.
35
36 (34) Ma, J.; Zhan, M.; Wang, K. Ultralightweight Silver Nanowires Hybrid
37
38
39 Polyimide Composite Foams for High-Performance Electromagnetic Interference
40
41
Shielding. ACS Appl. Mater. Interfaces 2015, 7, 563-576.
42
43
44 (35) Wen, B.; Cao, M.; Lu, M.; Cao, W.; Shi, H.; Liu, J.; Wang, X.; Jin, H.; Fang, X.;
45
46
Wang, W.; Yuan, J. Reduced Graphene Oxides: Light-Weight and High-Efficiency
47
48
49 Electromagnetic Interference Shielding at Elevated Temperatures. Adv. Mater. 2014,
50
51
26, 3484-3489.
52
53
54 (36) Kumar, A.; Alegaonkar, P. S., Impressive Transmission Mode Electromagnetic
55
56
57
Interference Shielding Parameters of Graphene-like Nanocarbon/Polyurethane
58
59
60
ACS Paragon Plus Environment
Page 25 of 34 ACS Applied Materials & Interfaces

1
2
3
4 Nanocomposites for Short Range Tracking Countermeasures. ACS Appl. Mater.
5
6 Interfaces 2015, 7, 14833-14842.
7
8
9 (37) Zhang, H. B.; Yan, Q.; Zheng, W. G.; He, Z.; Yu, Z. Z., Tough
10
11 Graphene-Polymer Microcellular Foams for Electromagnetic Interference Shielding.
12
13
14 ACS Appl. Mater. Interfaces 2011, 3, 918-924.
15
16 (38) Cao, M. S.; Yang, J.; Song, W. L.; Zhang, D. Q.; Wen, B.; Jin, H. B.; Hou, Z. L.;
17
18
19 Yuan, J., Ferroferric Oxide/Multiwalled Carbon Nanotube vs Polyaniline/Ferroferric
20
21 Oxide/Multiwalled Carbon Nanotube Multiheterostructures for Highly Effective
22
23
24 Microwave Absorption. ACS Appl. Mater. Interfaces 2012, 4, 6949-6956.
25
26 (39) Balandin, A. A. Thermal Properties of Graphene and Nanostructured Carbon
27
28
29 Materials. Nat. Mater 2011, 10, 569-581.
30
31 (40) Mir Mohammad Sadeghi, I. J., and Li Shi. Phonon-interface Scattering in
32
33
34 Multilayer Graphene on An Amorphous Support. PNAS 2013, 110, 16321-16326.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 26 of 34

1
2
3
4 FIGURES AND CAPTIONS
5
6
7
Figure 1. Raw diagram for the fabrication of carbon foam derived from bread
8
9
10
11 Figure 2. (a) Micro structure evolution of bread by changing the content of yeast and water, SEM
12
13 cross-section images of microscopic structures evolution of carbon foam: (b) water content keeps
14
15
16 as 55 ml per 100 g flour, and the dry yeast content is 0.5 g, 1.0 g, 1.5 g per 100 g flour from left to
17
18 right, (c) dry yeast content keeps as 1.0 g per 100 g flour, and water content is 50 ml, 55ml and 65
19
20
21 ml per 100 g flour from left to right, (d) Hierarchical pore structures, (e) Length scale of
22
23 hierarchical pores.
24
25
26 Figure 3. (a) XPS spectra of B500 and B2000 samples, (b) C1s XPS spectra of B500 and B2000
27
28
29 samples, (c) XRD pattern, (d) Raman spectrum and (e) Infrared spectra of samples carbonized at
30
31 500℃(B500), 1000℃(B1000), 1500℃(B1500) and 2000℃(B2000) respectively, (f) The 77 K N2
32
33
34 sorption isotherms and corresponding pore size distributions for large pores (BL, with low bulk
35
36 density) and small pores (BS, with high bulk density) samples.
37
38
39
Figure 4. (a) Stress–strain measurements of carbon foam with different bulk density carbonized at
40
41
42 1000℃, (b) Compressive moduli E of carbon foam carbonized at different temperature, bulk
43
44
densities of measured sample are all between 0.21~0.22 g/cm3, (c) left: a 100g weight standing on
45
46
47 a piece of bread, middle: a 100g weight standing on a carbon foam; right: the carbon foam
48
49
50 standing on a bamboo leaf.
51
52
53 Figure 5. (a) Permittivity and (b) dielectric loss tangent characterization of the samples (C30% and
54
55 C10%) in the 2~18 GHz range, (c) schematic representation of microwave transfer across the
56
57
58 hierarchical pore structure of CF, (d) EMI shielding efficiency of carbon foam (carbonized at
59
60
ACS Paragon Plus Environment
Page 27 of 34 ACS Applied Materials & Interfaces

1
2
3
4 1000℃, density is 0.22g/cm3): the thickness is 3 mm, 4 mm and 5 mm respectively, (e) electrical
5
6 conductivity of CF carbonized at 500℃, 1000℃, 1500℃ and 2000℃, (f) the comparison of SE,
7
8
9 microwave absorption (LA), and microwave reflection (LR) at f =9 GHz (the thickness of the
10
11 samples is 3 mm)
12
13
14 Figure 6. Thermal conductivity of carbon foam (a) at different carbonized temperature of 500℃,
15
16
17 1000℃, 1500℃ and 2000℃, insert picture is alcohol lamp flame burning a flower standing on a
18
19
thin carbon foam plate, (b) thermal conductivity carbonized at 1000℃ with different bulk density,
20
21
22 (c) Schematic illustration of contributions to thermal conductivity in the foam with hierarchical
23
24
pore structure, (d) burning an ethanol-soaked carbon foam results in a residue with a similar shape
25
26
27 as the original shape，showing its fine fire resistance.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 28 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Figure 1. Raw diagram for the fabrication of carbon foam derived from bread
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
Page 29 of 34 ACS Applied Materials & Interfaces

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45 Figure 2. (a) Micro structure evolution of bread by changing the content of yeast and water, SEM
46
47
48 cross-section images of microscopic structures evolution of carbon foam: (b) Water content keeps
49
50 as 55 ml per 100 g flour, and the dry yeast content is 0.5 g, 1.0 g, 1.5 g per 100 g flour from left to
51
52
53 right, (c) Dry yeast content keeps as 1.0 g per 100 g flour, and water content is 50 ml, 55ml and 65
54
55 ml per 100 g flour from left to right, (d) Hierarchical pore structures, (e) Length scale of
56
57
58 hierarchical pores.
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 30 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40 Figure 3. (a) XPS spectra of B500 and B2000 samples, (b) C1s XPS spectra of B500 and B2000
41
42
43 samples, (c) XRD pattern, (d) Raman spectrum and (e) Infrared spectra of samples carbonized at
44
45 500℃(B500), 1000℃(B1000), 1500℃(B1500) and 2000℃(B2000) respectively, (f) The 77 K N2
46
47
48 sorption isotherms and corresponding pore size distributions for large pores (BL, with low bulk
49
50 density) and small pores (BS, with high bulk density) samples.
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
Page 31 of 34 ACS Applied Materials & Interfaces

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Figure 4. (a) Stress–strain measurements of carbon foam with different bulk density carbonized at
27
28
29 1000℃, (b) Compressive moduli E of carbon foam carbonized at different temperature, bulk
30
31 densities of measured samples are all between 0.21~ 0.22 g/cm3, (c) Left: a 100g weight standing
32
33
34 on a piece of bread, middle: a 100g weight standing on a carbon foam; right: the carbon foam
35
36 standing on a bamboo leaf.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 32 of 34

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39 Figure 5. (a) Permittivity and (b) dielectric loss tangent characterization of the samples (C30% and
40
41 C10%) in the 2–18 GHz range, (c) Schematic representation of microwave transfer across the
42
43
44 hierarchical pore structure of CF, (d) EMI shielding efficiency of carbon foam (carbonized at
45
46
1000℃, density is 0.22g/cm3): the thickness is 3mm, 4mm and 5mm respectively, (e) Electrical
47
48
49 conductivity of CF carbonized at 500℃,1000℃,1500℃ and 2000℃, (f) The comparison of SE,
50
51
microwave absorption (LA), and microwave reflection (LR) at f =9 GHz (the thickness of the
52
53
54 samples is 3 mm)
55
56
57
58
59
60
ACS Paragon Plus Environment
Page 33 of 34 ACS Applied Materials & Interfaces

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21 Figure 6. Thermal conductivity of carbon foam (a) at different carbonized temperature of 500℃,
22
23
24 1000℃, 1500℃ and 2000℃, insert picture is alcohol lamp flame burning a flower standing on a
25
26 thin carbon foam plate, (b) Thermal conductivity carbonized at 1000℃ with different bulk density,
27
28
29 (c) Schematic illustration of contributions to thermal conductivity in the foam with hierarchical
30
31 pore structure, (d) Burning an ethanol-soaked carbon foam results in a residue with a similar shape
32
33
34 as the original shape，showing its fine fire resistance.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 ACS Applied Materials & Interfaces Page 34 of 34

1
2
3 Table of Contents Graphic
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27 A facile and green strategy for fabrication of lightweight yet stiff carbon foam with
28 tunable pore structure is proposed.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment