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Applications of Polymer, Composite, and Coating Materials

A Novel Method for Preparing Auxetic Foam from Closed-cell Polymer
Foam Based on Steam Penetration and Condensation (SPC) Process
Donglei Fan, Minggang Li, Jian Qiu, Haiping Xing, Zhiwei Jiang, and Tao Tang
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b02332 • Publication Date (Web): 31 May 2018
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8 A Novel Method for Preparing Auxetic Foam from Closed-cell Polymer
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10 Foam Based on Steam Penetration and Condensation (SPC) Process
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12 Donglei Fana,b, Minggang Li*a, Jian Qiua, Haiping Xinga, Zhiwei Jianga, Tao Tang*a
13 a
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of
14
Sciences, Changchun 130022, China
15 b
University of Science and Technology of China, Anhui 230026, China
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17
ABSTRACT: Auxetic materials are a class of materials possessing negative Poisson’s ratio. Here we established a novel method
18
for preparing auxetic foam from closed-cell polymer foam based on steam penetration and condensation (SPC) process. Using
19 polyethylene (PE) closed-cell foam as an example, the resultant foams treated by SPC process presented negative Poisson’s ratio
20 during stretching and compression testing. The effect of steam-treated temperature and time on the conversion efficiency of
21 negative Poisson’s ratio foam was investigated, and the mechanism of SPC method for forming re-entrant structure was discussed.
22 The results indicated that the presence of enough steam within the cells was a critical factor for the negative Poisson’s ratio
23 conversion in the SPC process. The pressure difference caused by steam condensation was the driving force for the conversion from
24 conventional closed-cell foam to the negative Poisson's ratio foam. Furthermore, the applicability of SPC process for fabricating
25 auxetic foam was studied by replacing PE foam by polyvinyl chloride (PVC) foam with closed-cell structure or replacing water
26 steam by ethanol steam. The results verified the universality of SPC process for fabricating auxetic foams from conventional foams
27 with closed-cell structure. In addition, we explored potential application of the obtained auxetic foams by SPC process in the
fabrication of shape memory polymer materials.
28 Keywords: Negative Poisson's ratio, steam treatment, polymer foam, polyethylene, polyvinyl chloride.
29
30
31 1. INTRODUCTION value of the obtained foam by this method is still small.
32 Metamaterial concept offers a promising route to develop Lisiecki et al.12 put forward mechanic-chemic-thermal process
33 the materials with unusual or unprecedented properties. to prepare open-cell polyurethane (PU) auxetic foam. The
34 Auxetic materials refer to a class of materials possessing foams were exposed to chemical solvent (acetone) after
35 negative Poisson’s ratio. They expand in the transverse tri-axial compression to soften the foam, then were stabilizing
direction when being stretched, while shrink under at 180 oC, and were set at 120 oC finally. This method can
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compression.1 Since the publication of the first report on prepare foam specimens with more homogeneous cell
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artificial auxetic foam materials in 1987,2 it has been paid structure. However, although the prepared auxetic foam has
38 much attention because of its novel properties and numerous good performance, the use of a large amount of volatile
39 potential applications. As auxetic materials possess excellent organic solvents brought environmental pollution and hidden
40 properties, such as high shear modulus and yield strength, trouble for production safety. What’s more, solvent removal,
41 large indentation resistance, good resilience, good anti-notch drying processes substantially increased the processing
42 performance and excellent fracture toughness, they have a complexity as well as processing time. In addition, the
43 broad application prospects in plenty of fields, such as sound obtained foams have a typical strain-dependent Poisson's ratio.
44 barrier, insulation, buffer, cushions, especially in the artificial Very recently, Li et al.16 have used environmentally friendly
45 disc, artificial blood vessels, sandwich panels, manufacturing and easily removed CO2 as processing agents to prepare
46 fasteners or seat belts, internal combustion engine catalyst auxetic open-cell foams with constant Poisson's ratio over
converter carrier materials.3-9 large deformation at room temperature. They found that the
47
In recent years, a variety of fabricating methods for introducing of styrene-acrylonitrile copolymer (SAN) into the
48 negative Poisson’s ratio foam (auxetic foam) have been PU matrix enhances the loading bearing capability of the
49 reported. For example, the auxetic foams from the foams with foam, which generates a constant negative Poisson's ratio over
50 open-cell or partially open-cell structure are generally large deformation for the prepared foam.16
51 prepared by bi-axial compression10 or tri-axial compression11 So far the research about the fabrication of auxetic foams
52 or mechanic-chemic-thermal process12, and the auxetic foams from the conventional closed-cell foams is few. Comparing
53 from closed-cell foams are prepared by high pressure or the structures of open-cell and closed-cell foams, it is more
54 vacuum.13 Lakes has firstly employed the tri-axial difficult to realize the conversion from conventional
55 compression method in preparing the negative Poisson’s ratio closed-cell foam to the negative Poisson's ratio foam, because
56 foam, and since then significant effort has been made to the cell wall (not rib in open-cell foams) in the closed-cell
prepare auxetic foams.14-16 Although the tri-axial compression foams needs to be transformed into re-entrant structure,
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equipment has been improved, the negative Poisson’s ratio different from the case of open-cell foam. Martz et al.13
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achieved the transformation from conventional closed-cell
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polyethylene (PE) foam to negative Poisson’s ratio foam under
3 high pressure or vacuum condition. In their work, the
4 processing temperature should be higher than softening
5 temperature of PE, at which the relaxation of PE and cell wall
6 bending of PE foam could be realized. Finally, the permanent
7 deformation of the cell structure was achieved by decreasing
8 the temperature and letting the specimen cool before the load
9 was removed. This method is relatively simple but can only
10 obtain negative Poisson's ratio in small deformation (32%
11 strain). Thus more exploration is urgently required to find the
12 novel method to prepare the negative Poisson’s ratio foam
material from closed-cell polymer foams.
13
In this work, we demonstrate a novel method for
14 fabricating negative Poisson’s ratio foam from closed-cell PE
15 foams. This method is based on steam treatment under
16 atmospheric pressure through water steam penetration and
17 condensation (SPC) process, so it is simple and green. As we
18 know, the cell wall of closed-cell polymer foam is composed
19 of polymeric film with various thicknesses, which shows
20 permeability to gas and deformability under some conditions.
21 In fact, the permeation rate (P) of small penetrants is
determined by P=D·S, where D is the diffusion coefficient and
22
S is the solubility of penetrant.17 As the thickness and
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crystalline state of polymer films strongly influence the
24 diffusion coefficient and solubility of penetrant, the
25 permeability of gas or liquid through polymer films will be
26 determined by these factors. Normally polymer films have
27 “double-edged sword” behaviour for the penetration or barrier
28 of gas, depending on the testing time. So the effect of
29 steam-treated temperature and time on the negative Poisson’s
30 ratio conversion efficiency was studied. The morphologies of
31 the original foam and the auxetic foam were compared. The
mechanism of SPC process for PE conventional foam
32
transforming into negative Poisson’s ratio material was
33
discussed. Finally the applicability of SPC process for
34 fabricating auxetic foam was studied by replacing PE foam by
35 polyvinyl chloride (PVC) foam with closed-cell structure or
36 replacing water steam by ethanol steam.
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2. EXPERIMENTAL SECTION
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2.1. Materials. Commercial closed-cell PE foams with 20, 30,
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and 45 expansion ratio were purchased from Shijiazhuang
40 Qihong Rubber Product Limited Company. The closed-cell
41 PVC foam with the density of 52 Kg/m3 was fabricated in our
42 laboratory.
43
44 2.2. Preparation of negative Poisson’s ratio foam by SPC
45 process. As shown in Fig. 1, steam penetration and
46 condensation (SPC) process was established to fabricate
47 auxetic foams from conventional closed-cell polymer foams.
In particular, first the PE foam was cut to approximately 10
48
cm x 10 cm x 10 cm in length, width and thickness,
49 respectively. And then the sample was put into the
50 environment of water steam stayed for a certain time at
51 specified temperature. Finally, it was taken out and let it cool
52 to obtain the PE auxetic foam. The auxetic foams prepared in
53 this method are uniform except the edge, which is very
54 important for the accuracy of Poisson's ratio value. The PVC
55 foam was treated with the same method. In some cases,
56 ethanol steam was used to replace water steam for treating PE
57 foam. In the following context, the OF-X represented the
original foam with an expansion ratio of X, STF-X represented
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the steam-treated foam with an expansion ratio of X, OHF-X
represented the oven-high-temperature-treated foam with an
expansion ratio of X, and ETF-X represented the
ethanol-treated foam with an expansion ratio of X. The
OHF-X-Y represented the oven-high-temperature-treated foam
with an expansion ratio of X at Y °C, and the STF-X-Y
represented the steam-treated foam with an expansion ratio of
X at Y °C. For example, the OF-20 meant the original foam
with an expansion ratio of 20, and STF-45-100 represented the
steam-treated foam with an expansion ratio of 45 at 100 °C.
As control, oven high temperature treatment was used to
study the mechanism of SPC process. In detail, the mass of the
foam specimen with different expansion ratio was weighed
before placing into the oven, and then heated at 100 °C for 6 h.
The treated sample (OHF-X) was weighed after the oven
treatment. The mass change of the specimens from steam
treatment and oven treatment was compared to determine
whether water steam entered the cell during the steam
treatment.
2.3. Characterization. For mechanical testing, the middle part
of the foam sample after SPC was selected and cut into
rectangular sample with approximately 5 cm x 1.5 cm x 0.6
cm in length, width and thickness, respectively. Firstly, a line
which is vertical to the direction of stretch was drawn on the
rectangular sample. And the original length (l0) and thickness
(t0) were measured with a vernier caliper. Then, the
rectangular sample was tested with a tensile rate of 5 mm/min
by the electronic universal tensile tester (Changchun
Intelligent Instrument and Equipment Limited Company).
During the test, the length (l) and thickness (t) of the drawn
line were measured under different engineering strains. The
longitudinal strain (εl) and the thickness direction strain (εt)
were calculated by the following formula:
l - l0
εl= (1)
l0
t − t0
εt= (2)
t0
Poisson's ratio (the thickness direction Poisson's ratioν t)
was calculated by the classical definition:
εt
ν t=-  (3)
εl
Volume compression factor was the value of the final
density divided by the original density. And the density was
measured in buoyancy method. For STF, it was the value of
the density of steam-treated foam divided by the original foam
density. For OHF, it was the value of the density of
oven-high-temperature-treated foam divided by the original
foam density.
The tensile and compression testing was carried out with
a tensile rate of 5 mm/min by the electronic universal tensile
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tester (Changchun Intelligent Instrument and Equipment conversion from conventional closed-cell foams to negative
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Limited Company). The Poisson's ratio value given in the Poisson's ratio foams, and the greater the expansion ratio of
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the foams is, the easier this conversion is. Fig. 3 shows the
4 SEM images of the foam specimens before and after steam
5 treatment. It can be seen that the untreated foams have a full
6 cell structure, and the cell walls are straight. The cell wall
7 thicknesses of three PE foams with 20, 30 and 45 expansion
8 ratio are 6.1 µm, 4.4 µm and 2.2 µm, respectively. The
9 particulate matter on the cell walls are inorganic particles
10 Figure 1. The schematic drawing of SPC process for the added by the manufacturers as foaming nucleating agents,
11 preparation of negative Poisson’s ratio foam. which was verified by TGA measurements. After the steam
12 treatment at 100 °C for 6 h, the full cell of the foams shrink
manuscript were the average values of the treated foams under inward, and the cell walls are obviously bent, as a result, the
13
the same conditions after five times measurements. The re-entrant structure appears. The transformation degree of
14 re-entrant structure from normal cell structure is more obvious
standard deviation is between 0.028 and 0.179. We presented
15 the standard deviation of the Poisson's ratio of the STF-45-100 in the foams with higher expansion ratio, which is consistent
16 as an example in Fig.S1 in SI. with the results of Fig. 2.
17 Morphologies of the foam specimen were observed by Actually, we observed the following phenomenon during
18 Phenom ProX desktop scanning electron microscopy (SEM) the fabrication of auxetic foams: After the PE foam was put
19 of Fenna Scientific Instruments Limited Company. The cross into the environment of water steam at specified temperature,
20 sections of all specimens were exposed by cryo-fracturing the volume of the foam expanded quickly. When the foam was
21 under liquid nitrogen. taken out, the foam quickly shrunk in several seconds at room
22 The melting point of the foam before and after steam temperature, and then the shape of auxetic foams did not
treatment was measured by METTLER TOLEDO's DSC1 change. Now there are two questions about the fabrication
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differential scanning calorimeter. The 5-10 mg foam specimen process of auxetic foam by SPC process: What is the driving
24 force for strong shrinking of PE foam after fabrication process
was loaded in aluminum pans and heated under a nitrogen
25 atmosphere. A first heat scanning was carried out from 25 °C of auxetic foam by SPC process? Why can the shape of shrunk
26 to 180 °C at a rate of 10 °C/min, and the specimen was held PE foam be kept? Fig. 4 presents a schematic drawing for
27 for 5 min in the molten state to eliminate thermal history. Then possible mechanism of preparing the negative poisson's ratio
28 it was cooled to 25 °C at a rate of 10 °C/min and held for 5 foam by SPC process. The key factors should include
29 min. Finally, a second heat scanning was executed with penetrability of water steam through the cell wall, and
30 heating to 180 °C at a rate of 10 °C/min. deformation ability for shrinking stage of the foam and
31 The liquid water content was measured by SDTQ600 shaping ability for keeping re-entrant structure of foam cell in
32 thermal gravimetric analyzer made in TA Instruments. A heat the final cooling stage. In the cases of semi-crystalline
scanning was carried out from 25 °C to 900 °C at a rate of 10 polymer foams, the above factors are closely related to
33
°C /min under air atmosphere. crystalline state and crystallization behaviour of PE foams.
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35 3. RESULTS AND DISCUSSION
36 Fig. 2 shows the relationship between the Poisson's ratio
37 and engineering strain of the original foam (OF-X, X
38 represents expansion ratio of foam) and steam-treated foam
(STF-X specimens) by SPC process (treating conditions: at
39
100 °C for 6 h; see the detailed process in the experimental
40 section). It can be seen that the Poisson's ratio value of the
41 original foam is positive, while the Poisson's ratio of the
42 steam-treated foam becomes small and even negative value.
43 The minimum Poisson's ratios of the steam-treated foam
44 specimens with 20, 30 and 45 expansion ratio in the stretch
45 testing are -0.278, -0.439 and -0.487, respectively. When
46 being compressed, the minimum Poisson's ratios of the
47 steam-treated foam specimens with 20, 30 and 45 expansion
48 ratio are -0.026, -0.090 and -0.118, respectively. The Poisson's
49 ratio increases with engineering strain in both stretch testing Figure 2. The relationship between Poisson's ratio and
and compression testing. The negative Poisson’s ratio
50 engineering strain of PE foam specimens with different
behavior vanishes when engineering strain in the stretch
51 testing increases to 0.201, 0.303, and 0.604 for foam
expansion ratio before and after steam treatment (The
52 steam-treated time and temperature were 6 h and 100 °C,
specimens with 20, 30 and 45 expansion ratio, respectively. respectively).
53 This phenomenon has been observed in the previous
54 reports for negative Poisson’s ratio foam,12,13,18 in which the
55 auxetic foam can be obtained only within 0.322 engineering
56 strain.13 In contrast, the negative Poisson's ratio behaviour can
57 maintain to 0.604 engineering strain in this work. The above
58 results indicate that the steam treatment realized the
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cooling. The higher the increased weight of the steam-treated
2
foam is, the greater the volume compression factor after
3
cooling. These results illustrate that water steam has
4 penetrated into the foam inside during the steam treatment.
5 After some time, the internal and external water steam
6 concentration reaches equilibrium. When the sample is taken
7 out from the steam environment, the outside temperature drops
8 quickly. At the same time, the water steam within the cell is
9 rapidly condensed, which result in rapid pressure drop inside
10 the foam cells. As a result, the pressure outside the cell (1 atm)
11 is significantly greater than the pressure inside the cell,
12 therefore the cells rapidly shrink and invaginate because of the
pressure difference, and the re-entrant structure is formed.
13
Therefore, the driving force for the formation of re-entrant cell
14 structure results from the pressure difference between the
15 outside of cell and the inside of cell during SPC process.
16 Obviously both the treatment time and treatment temperature
17 during SPC process will affect the formation of pressure
18 Figure 3. SEM images of PE foam specimen before and after difference between the inside of cell and the outside of cell.
19 steam treatment ((a), (b) and (c) original foams with the The above results come from “double-edged sword” behaviour
expansion ratio of 20, 30 and 45, respectively; (d), (e) and (f)
20 of polymer films for the penetration or barrier of gas,
steam-treated foams with the expansion ratio of 20, 30 and 45, depending on the observation time. A gas can penetrate
21 respectively. The steam treatment time and temperature were 6
22 through polymer film in a long observation time, but the gas
h and 100 °C, respectively). will be obstructed in a short observation time. In the SPC
23
process, the transformed foam structure is fixed after the
24 cooling of the foam, probably due to the partial
25 recrystallization of cell wall, and finally the conversion from
26 positive Poisson's ratio to negative Poisson's ratio is realized
27 ultimately.
28 As we know, the key for preparing auxetic foam with
29 negative Poisson’s ratio is that the cell structure is transformed
30 into re-entrant structure.2 It can be seen that both the stage for
31 steam penetration through cell wall and the stage for steam
32 condensation within the cell are two key processes for the
formation of re-entrant structure in this method. Under the
33
same steam conditions, the transformation efficiency of
34 Figure 4. Schematic drawing for possible formation re-entrant structure should be determined by steam
35 mechanism of re-entrant structure from closed-cell foams by penetrability, and deformation ability and shaping ability of
36 SPC process. cell wall. These properties mainly depend on the conditions of
37 steam treatments (temperature and time). The temperature for
38 Generally a part of crystalline fraction of cell wall in the steam treatment strongly influences the crystalline state and
PE foams will melt during steam treatment if the steam
39 deformation ability of the foam matrix during SPC process.
temperature is high, strongly depending on the specific
40 temperature and time for steam treatment, which lead to
41 Table 1 The relationship of volume compression factor with
softening of the cell wall (Fig. 5a). So the cells expand due to mass change fraction of PE foams with different expansion
42 expansion of the gas inside cells. Meanwhile the penetration of ratio after steam treatment and oven treatment.
43 water steam into the inside of cells will occur during steam
44 treatment. In order to confirm the penetration of water steam Expansion ratio 20 30 45
45 during steam treatment, the mass change of the steam-treated
Mass change after oven treatment
46 foam and oven-treated foam at the same temperature (100 °C)
at 100 °C for 6 h (wt %)
1.6 2.0 2.1
47 for the same treatment time (6 h) was compared to explore the
48 mechanism for the formation of auxetic foam with negative Volume compression factor 1.0 1.0 1.0
Poisson’s ratio (Table 1). From Table 1, it can be seen that the
49 Mass change after steam treatment
19.2 42.6 63.1
mass change of the foam specimen before and after oven
50 treatment at 100 °C is very small. There is also no significant
at 100 °C for 6 h (wt %)
51 change in the volume of foam specimen before and after Volume compression factor 1.3 5.1 5.9
52 oven-high-temperature treatment, and the volume compression
53 factor of OHF is approximately 1. Importantly, no negative
54 Poisson’s ratio behaviour appears in the foams after oven
55 treatment under the mentioned conditions. In contrast, the
56 mass of foam specimens after water steam treatment increases,
57 especially the foams with 45 expansion ratio. Meanwhile these
58 steam-treated foams present significant volume shrinkage after
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16 Figure 7. The relationship between Poisson's ratio and
17 engineering strain of PE foam specimens at different treatment
18 time (The steam treatment temperature was 100 °C and the
19 expansion ratio was 45 times).
20
21
22 Figure 5. (a) DSC heating curves of PE foam specimen before Fig. 6 shows the relationship between the Poisson's ratio
23 (OF-x) and after (STF-x) steam treatment (Treatment and the engineering strain of foam specimens by steam
24 conditions: 100 °C for 6 h); (b) DSC first heating curves of treatment at different temperatures. The Poisson's ratio of the
OF-45 (OF-45-1UP) and the heat-treated foam specimens at foam specimen decreases with the increase of treatment
25
100 °C (OHF-45-100-1UP), 80 °C (OHF-45-80-1UP) and temperature. The negative Poisson’s ratio begins to appear
26 60 °C (OHF-45-60-1UP); (c) The test program of (d) and (e); when the treatment temperature reaches 80 °C, and the foams
27 (d) DSC curves of OF-45 annealed at 100 °C (OF-1-45-100: show an obvious negative Poisson's ratio behavior when
28 black line-the first heating curve from 25 to 100 °C, blue treated at 100 °C. From the DSC heating curve (Fig. 5a), it can
29 line-cooling curve from 100 to 25 °C after annealing at 100 °C be seen that the temperature has a key effect on the crystalline
30 for 1 h, red line-the second heating curve from 25 to 180 °C); state of the PE foam, which will influence the deformability of
31 (e) DSC curves of OF-45 annealed at 60 °C (OF-1-45-60: cell wall and the permeability of water steam through cell wall.
32 black line-the first heating curve from 25 to 60 °C, blue The fraction of melted crystal is very low at 60 °C, and the PE
33 line-cooling curve from 60 to 25 °C after annealing at 60 °C foam partially melts at 80 °C. A large of the crystalline
34 for 1 h, red line-the second heating curve from 25 to 180 °C). fraction will melt at 100 °C and completely melt at 112 °C. On
The heating or cooling rate was 10 °C/min in all the the other hand, the saturated vapor pressure of water will
35
measurements. increase with the temperatures, for example, 19.9 kPa at 60 °C,
36 47.4 kPa at 80 °C and 101.3 kPa at 100 °C, respectively.
37 Hence, the steam treatment at 100 °C is more efficient to
38 realize the conversion of negative Poisson’s ratio in the
39 process of steam treatment.
40 As mentioned-above, polymer films show “double-edged
41 sword” behavior for the penetration or barrier of gas,
42 depending on the testing time. The permeation of water steam
43 through the cell wall (PE film) is a slow process, which is
44 controlled by water molecule diffusion and solubility of water
in the PE matrix.19,20 Therefore the water steam treatment time
45
should have an important effect on the negative Poisson's ratio
46
conversion. Fig. 7 shows the relation between Poisson's ratio
47 and engineering strain of the foam specimen by steam
48 treatment at 100 °C for different treatment time. It can be seen
49 that Poisson's ratio decreases gradually with the increase of
50 steam treatment time from 2 h to 6 h, and reaches the lowest
51 value after treating for 6 h, then gradually increases with
52 Figure 6. The relationship between Poisson's ratio and
extending treatment time. This phenomenon is ascribed to that
53 engineering strain of PE foam specimens at different treatment
the evaporation and condensation of water steam is a
54 reversible process, in which a part of water steam within the
temperatures (The expansion ratio was 45 times and the steam
55 cell starts to condense into liquid water due to supersaturation.
treatment time was 6 h).
The longer the treatment time is, the higher the content of
56
liquid water within the cell is (Fig. 8). When the foam is
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cooled, the presence of liquid water partly counteracts the temperature in the steam treated foams should mainly result
2
volume shrinkage of the foams. Therefore, the efficiency of from recrystallization of PE.
3
Fig. 5d and 5e compare the effect of annealing
4 temperature on the crystallization behavior and melting
5 behavior of PE foams with the expansion ratio of 45. It can be
6 seen that the sample annealed at 100 °C for 1 h shows a strong
7 exothermic peak during cooling process and double
8 endothermic peaks during reheating process, similar to that of
9 OHF-45-100-1UP (Fig. 5d vs Fig. 5b). Compared to the DSC
10 curve of OF-45-1UP in Fig. 5b, the sample annealed at 100 °C
11 for 1 h shows a new melting peak in the left side of the main
12 melting peak (OF-1-45-100-2UP in Fig. 5d). This new melting
peak should result from recrystallization of melted fraction of
13
PE foams during cooling process, which provide shaping
14 ability for keeping re-entrant structure of foam cell in the final
15 cooling stage. In contrast, the sample annealed at 60 °C for 1 h
16 shows a very weak exothermic peak during cooling process
17 and a similar endothermic behavior to that of OHF-45-60-1UP
18 Figure 8. The mass change vs treating time for the PE foam (Fig. 5e vs Fig. 5b) during reheating process. This means that
19 with 45 expansion ratio (The steam treatment temperature was the shaping ability for keeping re-entrant structure of foam cell
20 100 °C). is weak in the samples annealed at 60 °C. In addition, as
21 mentioned above, the deformability of cell wall is also weak at
22 lower temperature, and there is no enough amount of water
steam within the cells of PE foam to form a driving force for
23
the conversion of re-entrant structure from conventional foam
24 structure during cooling, so no negative Poisson's ratio
25 behavior appears in the steam-treated foams at 60 °C.
26 The deformation and shaping (or shape fixation)
27 mechanism of auxetic foam in this work is similar to the
28 process for steam-chest molding of expanded polypropylene
29 (EPP) foams. Zhai et al. stated the formation mechanism of
30 interbead bonding during EPP bead processing21 and used
31 DSC to simulate bead foaming process22. The authors
32 considered that the high temperature during steam-chest
molding can melt some of the original crystal, and softened
33
polymer matrix is conducive to the expansion and welding of
34 beads. In fact, the high temperature steam treatment causes the
35 beads expand, and the EPP beads impinge with each other,
36 then deform and eventually achieve welding in a limited mold
37 Figure 9. DSC first heating curves of OF-20 and the volume. The molded bead samples were then stabilized by
38 heat-treated foam specimens at 100 °C (OHF-20-100-1UP), cooling to obtain EPP ware. More importantly, the
39 80 °C (OHF-20-80-1UP) and 60 °C (OHF-20-60-1UP). temperature used for the molding of EPP beads is in between
40 the temperature for the lower melting peak and the
41 the negative Poisson's ratio conversion decreases when the temperature for the higher melting peak (the primary melting
42 steam treatment time surpasses 6 h. peak). The reason is that the EPP beads can weld together
In addition, the temperature for steam treatment also through interfacial diffusion due to partial melting of EPP and
43
influences recrystallization ability after shrinking, which the following recrystallization, but the foam cell structure can
44 determines the shaping ability of the resultant foam. As be kept. If the temperature for steam-chest molding is too high,
45 mentioned above, the deformation ability for shrinking stage all original crystals will completely melt, and also the cell
46 of the foam and shaping ability for keeping re-entrant structure structures of the EPP bead foam will be destroyed.
47 of foam cell are closely related to crystalline state and For the SPC process in this work, the melting of part
48 crystallization behavior of PE foams. Fig. 5b shows DSC crystals softens PE matrix during the steam treatment process,
49 heating curves (the first heating run) of the heat-treated foam which facilitates the diffusion of water vapor and the
50 specimen at 100, 80 and 60 °C for 6 h, simulating the steam deformation of PE matrix. The pressure difference caused by
51 treatment process. Compared to the DSC curves of original steam condensation makes the foam shrink quickly during
52 foams (OF-45), a new broad melting peak appears in the left cooling process. Meanwhile, the crystals formed after cooling
side of the main melting peak in all the foams treated by are used to fix the shape. The melting degree of the original
53
heating treatment at three temperatures, which is similar to the crystals and the crystals formed due to cooling increase with
54 cases of steam treatment (Fig. 5a). A similar phenomenon was steam treatment temperature. Hence, the steam treatment at
55 observed in the PE foams with the expansion ratio of 20 (Fig. 100 °C is more efficient to realize the conversion of negative
56 9). This result shows that the broad melting peak at the lower Poisson’s ratio in the process of steam treatment. In the whole
57 process, the steam treatment temperature is lower than Tm
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(108 °C, the main melting peak in DSC curves), meaning that
2
the crystalline structure formed from the recrystallization of
3
melted crystals determines the shaping ability, and the primary
4 crystalline structure associated with the higher temperature in
5 DSC is kept to maintain the cells structure.
6
7 The cyclic mechanical test was conducted to study the
8 change of Poisson's ratio. It can be seen from Fig. 10a and Fig.
9 10b that the auxetic foam can recover its original size and
10 shape after stretch testing and compression testing at small
11 engineering strain (0.1) for 4 cycles, and the Poisson's ratio is
12 basically unchanged. As the times of cycles increases, the
recovery performance of auxetic foam decreases and the
13
Poisson's ratio increases in some degree. When the
14 engineering strain is increased to 0.2, the recovery
15 performance of the auxetic foam significantly weakens, and Figure 12. The relationship between Poisson's ratio and
16 the Poisson's ratio greatly increases with the increase of the engineering strain of PE foam specimens of 45 expansion ratio
17 number of cycles. The larger the engineering strain is, the treated under ethanol steam (the steam treatment temperature
18 more obvious this trend is. and time were 78 °C and 6 h, respectively).
19
20
21
22
23
24
25
26
27
28
Figure 10. The relationship between the minimum of Poisson's
29 ratio and cycle index at different engineering strain in (a)
30 stretch testing and (b) compression testing.
31
32
Figure 13. Comparison for Poisson's ratio vs engineering
33
strain for PVC and PE foam specimens before and after steam
34 treatment (STF-PVC: The steam treatment temperature and
35 time were 100 °C and 6 h, respectively; STF-PE: The steam
36 treatment temperature and time were 100 °C and 6 h,
37 respectively).
38
39
40
41
42
43
44
45
46
47
48 Figure 11. The relationship between the minimum of Poisson's
49 ratio and oven treatment time for foam samples in (a) stretch
50 testing and (b) compression testing at different treatment
51 temperatures. (c) The relationship between the Poisson's ratio
52 and engineering strain for treated auxetic foam samples under Figure 14. SEM images of PVC foam specimens (a) before
53 different humidity for different treatment time (code name and (b) after steam treatment.
54 “30-24” represented auxetic foam samples treated in ambient
humidity of 30% for 24 h, and so on).
55 The thermal stability and moisture stability of the
56 prepared auxetic samples were investigated. The auxetic foam
57 samples were treated in an oven at different temperature for
58 different treatment time. Fig. 11 shows the relationship
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between the minimum of Poisson's ratio and oven treatment form a bilayer specimen. Based on the principle of SPC
2
time for foam samples in stretch testing (Fig. 11a) and method, the layer of PE auxetic foam will dramatically swell
3
compression testing (Fig. 11b) at different treatment
4 temperatures. It is found that auxetic foam can maintain
5 long-term stability when treated at 20 °C. However, the
6 minimum of Poisson's ratio rapidly increased when treated at
7 40 °C and 60 °C for 1 h, and this phenomenon was more
8 obvious at 60 °C. This is due to the presence of some liquid
9 water within the auxetic foams. The water will become water
10 steam during the heating process, which causes the foam
11 expands and the re-entrant structure shows a certain recovery
12 to normal cell structure. Extending the processing time, the
Poisson's ratio tends to be stable and still retains the
13
characteristic of auxetic foam. We will further improve the
14 temperature stability in the future work.
15 In order to investigate moisture stability of the prepared
16 auxetic samples, the STF-45-100 was treated at 30%, 50% and
17 70% humidity for 24 h and 48 h, respectively. Fig. 11c shows
18 the relationship between the Poisson's ratio and engineering
19 strain for auxetic foam samples under different humidity for
20 different treatment time. It can be seen that the results under Figure 15. The shape memory property of bilayer specimen of
21 different humidity are very close, meaning that the humidity PE auxetic foam/polyurethane film: (a), (b) and (c) The bilayer
22 has no significant effect on the Poisson's ratio of the auxetic specimen was put in hot water at 100 °C; (d), (e) and (f) The
foams. So the prepared auxetic foam has good humidity bilayer specimen was taken out and kept at room temperature.
23
stability.
24 We further study the applicability of SPC process for
25 when it is put in hot water or shrink when taken out at room
fabricating the auxetic foams from closed-cell polymer foams, temperature, while the layer of PU changes a little during the
26 for example, water steam is replaced by ethanol steam. Fig. 12 above processes. As a result, the shape of bilayer specimen
27 shows the relationship between the Poisson's ratio and will change with the ambience. Fig. 15 shows the change of
28 engineering strain of ethanol steam-treated foam at 78 °C. It the shape of the bilayer specimen with the environmental
29 can be seen that the obtained foam shows a lower negative temperature. When the bilayer specimen was put into the hot
30 Poisson's ratio than that of STF-45 treated at 80 °C. water at 100 °C, the sample quickly bended to form loop shape
31 Considering the influence of treating temperature, the (Fig. 15a-15c). After the sample was taken out from hot water,
32 deformation ability of PE foams in the two cases should have the sample rapidly deform to the original shape (Fig. 15d-15f).
a similar ability due to the close treating temperature.
33 This confirms that the bilayer specimen of PE auxetic
However, the saturated vapor pressures of water (47.4 kPa at foam/PU film possesses the shape memory properties.
34 80 °C) and ethanol (101.3 kPa at 78 °C) at treating
35 temperature are different. On the other hand, the penetration 4. CONCLUSIONS
36 process of gas through polymer films is determined by In summary, we demonstrated a novel method based on
37 solubility and diffusion of gas.23 The solubility of ethanol in SPC process to prepare polymer auxetic foam with the
38 PE film is much higher than that of water.23 As a result, more re-entrant structure in this work. The presence of the water
39 ethanol steam penetrates into the cell inside of PE foam, and a steam within the cell was a critical factor for the negative
40 strong driving force for the transformation of re-entrant Poisson’s ratio conversion in the process of steam treatment,
41 structure is formed. At the same time, the PE film that and the pressure difference caused by steam condensation was
42 includes some ethanol molecules will be easily deformed due the driving force for the transformation from conventional
to plasticization of ethanol. Thus the ethanol steam treatment foam to the auxetic foam. Under the same steam conditions,
43
is more efficient than water steam treatment to fabricate the transformation efficiency of re-entrant structure was
44 auxetic PE foam. The SPC process is also applied in determined by steam penetrability, deformation ability and
45 closed-cell PVC foam to fabricate the auxetic foams (Fig. 13 shaping ability of cell wall. These characteristics mainly
46 and 14), which verifies the universality of this method. As the depended on the properties of polymer matrix and steam
47 PVC foam used in the experiment is brittle, and it breaks when properties, such as crystalline state of polymer matrix and
48 stretched in large strain, so Poisson's ratio value is not penetration behavior of steam in polymer matrix. Therefore,
49 obtained when the engineering strain is beyond 0.408. the conditions for steam treatment, including treating
50 From the above results, it is clear that an amount of water temperature and treating time, strongly influenced the
51 is kept in the inside of the obtained PE auxetic foam by SPC conversion from conventional foam to negative Poisson's ratio
52 method. The water inside the foam will vaporize or condense foam. In a word, the SPC process provided a novel specific
with the environmental temperature; as a result, the auxetic
53 route for fabricating negative Poisson's ratio materials from
foam will expand or shrink with the change of environmental closed-cell polymer foams under atmospheric pressure. In
54 temperature. This behavior can be applied in the fabrication of addition, the obtained auxetic foams by SPC process showed
55 shape memory materials from the auxetic foam. Firstly PE some potential application, such as the fabrication of shape
56 auxetic foam was adhered with polyurethane (PU) film to memory polymer materials.
57
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2 ■ ASSOCIATED CONTENT (13) Martz, E. O.; Lee, T.; Lakes, R. S.; Goel, V. K.; Park, J.
Supporting Information B. Re-entrant Transformation Methods in Closed Cell Foams
3 Cellular Polymers 1996, 15, 229-249.
4 The Supporting Information is available free of charge on the (14) Li, Y.; Zeng, C. On the Successful Fabrication of Auxetic
5 ACS Publications website. Polyurethane Foams: Materials Requirement, Processing
6 Strategy and Conversion Mechanism Polymer 2016, 87,
7 The relationship between Poisson's ratio and engineering 98-107.
8 strain of PE foam specimen with 45 expansion ratio after (15) Bezazi, A.; Scarpa, F. Mechanical Behaviour of
steam treatment. Video showing the shape memory property
9 Conventional and Negative Poisson’s Ratio Thermoplastic
of the bilayer specimen of PE auxetic foam/PU film. (AVI)
10 Polyurethane Foams Under Compressive Cyclic Loading Int. J.
11 Fatigue 2007, 29, 922-930.
■ AUTHOR INFORMATION (16) Li, Y.; Zeng, C. Room-Temperature, Near-Instantaneous
12 Corresponding Authors Fabrication of Auxetic Materials with Constant Poisson’s
13 *E-mail:ttang@ciac.ac.cn. Ratio over Large Deformation Adv. Mater. 2016, 28,
14 *E-mail: lmg@ciac.ac.cn. 2822-2826.
15 (17) Dimitroulas, G. D.; Badeka, A. B.; Kontominas, M. G.
16 ORCID Permeation of Methylethylketone, Oxygen and Water Vapor
17 Tao Tang: 0000-0002-1887-0579 through PET Films Coated with SiOx: Effect of Temperature
18 and Coating Speed Polym. J. 2004, 36, 198-204.
19 Notes (18) Clausen, A.; Wang, F.; Jensen, J. S.; Sigmund, O.; Lewis,
The authors declare no competing financial interest.
20 J. A. Topology Optimized Architectures with Programmable
21 ■ ACKNOWLEDGMENTS Poisson’s Ratio over Large Deformations Adv. Mater. 2015,
22 27, 5523-5527.
(19) Lee, W. M. Water Vapor Permeation in Closed Cell
23 The financial supports from National Natural Science
Foams J. Cell. Plast. 1973, 9, 125-129.
24 Foundation of China (51233005, 51573179 and 21304089)
(20) Waack, R.; Alex, N. H.; Frisch, H. L.; Stannett, V.;
25 and the Ministry of Science and Technology of China
(2015AA033901) are greatly appreciated. Szwarc, M. Permeability of Polymer Films to Gases and
26 Vapors Ind. Eng. Chem. Res. 1955, 47, 2524-2527.
27 ■ REFERENCES (21) Zhai W.; Kim Y. W.; Jung D. W.; Park C. B.
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