go graphenewith - trustwell · 2018-02-13 · 300% stress (mpa) tearstrength (n/mm) nature rubber...
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graphene
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What is graphene (GE) ?
almost no weight
100x stronger
than steel
Supper conductor
The flat film composed of carbon atoms in form of hexagonal honeycomb lattice, a two-dimensional material which is only one carbon atom thick.
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GE CNT Cu
Young's modulus(GPa) 1050 450 128
Density g/cm3 1.06 1.8 8.96
Thermal conductivity W/m·K 5300 3000 401
Electrical conductivity S/cm 106 105 105
Electron mobility cm2/(V·s) 15000 10000 30
Specific surface area(m2/g) 2600 2000 --
Why GE is ideal for rubber reinforcement?
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Test sample Tensile (MPa)Elongation at
break(%)300% stress
(MPa)Tear strength
(N/mm)
Nature Rubber (NR) 17.1 579 2.4 32.7
2% CB-NR 18.2 586 2.6 33.6
2% CNT- NR 18.6 534 3.3 37.7
2% GE-NR 25.2 564 6.6 49.2
effective (GE vs. CB) 7 -2 21 18
Why GE is ideal for rubber reinforcement?
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Dispersing of GE into Rubber
Structure control of GE dispersed into Rubber
i.e. isolated network forming …
Bottleneck
Why we don’t see yet so much GE be used in compounding?
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graphene/rubber
composite
preparation
technology
available
mechanic mixing
solution mixing
latex mixingIn situreduce
Simple process, scattered difficulties, mostly non-real graphene composite materials.
Vorbeck Materials 2010 patent(WO2010115173-A1;EP2414286-A1; US2012142832-A1;
KR2012107044-A; CN102612490-A)
Organic solvents, potentialenvironmental issue,
Princeton University 2010 patented technology (US7745528)
Water system, environmental friendly, graphene sheet dispersed thinner than
2 nanometers.
Sichuan University patented technology(ZL2010100191018.6)
What technology we have to disperse GE into Rubber?
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Polymer Research Institute
Chengdu Trustwell New Material Co., Ltd.
Latex mix, in situ reduced GE Rubber component
Patent: ZL2010100191018.6
Icebreaking technology for dispersing into rubber – open door to applications
共混
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Icebreaking technology for dispersing into rubber – comments of academy
Dr. RS Ruoff comments in Macromolecules, 2012, 45, 6045
Elongation at break and tensile strength for SBR/C filler composites relative to neat SBR
1. GE is the most effective modifier. MLG, TRGO, CRGO which less than 10
layers is obviously effctive than EG which more than 60 layers.
2. Latex mix, in situ reduce GE rubber composite is the only way for rubber
reinforcement.
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Liu Yandong, Vice Prime Minister
visits on 3rd Nov. 2017
Li Keqiang, Prime Minister visits on 28th Apr. 2016
Icebreaking technology for dispersing into rubber – attention from management
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Process Ready
≤ 3 layer atom
thickness
Isolated network
What makes outstanding?
3
uneven disperse
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Process Ready
What makes outstanding?
difficult handling
almost no weight
Easy disperse in matrix
rubber like
condition
uniform disperse master batch
1/3
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What makes outstanding?
100x strong
than steel
Super conductor
2 D material
2/3≤ 3 layer
atom thickness
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What makes outstanding?
GE isolation network and latex particles relationship under lens GE flake in NR latex under lens
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The size of the conductive network is comparable to the size of the latex particles, uniformly distributed in the NR
matrix at the submicron level
What makes outstanding?
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Latex mix, in situ reduce Twin roller mixing
Graphene dispersion in NR after shearing
What makes outstanding?
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Higher content of GE
5.15 vol% GE
What makes outstanding?
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Isolated network forming
What makes outstanding?
thermal conductive
gas barrier
electrical conductive
3/3
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NRLGES: latex mixing - in situ reduction + hot pressing
NRLGES-TR: latex mixing – in situe reduce + twin roller mix +
hot pressing
NRGE-TR: twin roller mix
NRGE-HM: Haake mix
Percolation parameters φc (vol%) s
NRLGES 0.62 1.01
NRLGES-TR 4.62 1.05
NRLGE 0.90 1.09
NRLGE-TR 4.65 1.01
s
c )(0
具有GE隔离网络的GE/NR逾渗阀值为0.62 vol%。当GE含量为1.78 vol%
时,导电率为 0.03 S/m,比传统方法高5个数量级。
Superb electronics conductivity associated with isolated network
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Permeability of the three gases investigated at T=25 0C for a) the non-segregated morphology and b) the segregated morphology as a
function of volumetric fraction of graphene.
Superb gas barrier associate with isolated network
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competitor
TRUSTWELL
What makes outstanding?
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S1(S2p3/2A)161.7 eV, polysulfide bond or elemental sulfur–C-Sx-C
S2(S2p3/2B) 163.8 eV, carbon-sulfur bond C-S
Graphene can change the path of the sulfidation
reaction, react with sulfur to form C-S bond,
reduce the content of polysulfide bond in the
rubber vulcanization system and form more C-S
bonds.
XPS S2p谱图
The atomic composition ratio of S1 and S2
Interfacial molecular interaction between galvanized graphite and natural rubber
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The diffraction peak: -C-Sx-C, with the introduction of graphene,
the local electron cloud density weakened and the diffraction
peak disappeared, suggesting that the number of sulfur atoms in
polysulfide-C-Sx-C decreased.
SAXS
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Stress-strain curve and selected WAXD patterns collected during stretching and retraction of sulfur vulcanized natural rubber (NR-S) at 0 oC.
Strain-induced crystallization is the main reason why rubber has excellent mechanical properties.
When the elongation is 3.5, NR / GE appears crystalline diffraction rings. The blank samples
and CNT system is not obvious.
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Strain-induced crystallization
Ozbas B, Toki S, Hsiao B S, et al. Strain‐induced crystallization and mechanical properties of functionalized graphenesheet‐filled natural rubberJournal of polymer science part B: Polymer physics, 2012, 50(10): 718-723.
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Equatorial diffraction profiles taken from 2D WAXD patterns at selected extension ratio of RGE, (b)
crystalline as a function of extension ratio for unfilled and filled NR composites
Why GE has so effective in reinforcement?
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Experimental conditions:
Spline: Rectangular Spline (cut in the middle)
Instrument: MTS-810
Frequency: f = 3HZ
Temperature: T = 20oC
Maximum fatigue strain:εmax=20%, 30%, 40%, 50%
By testing the fatigue crack growth rate of natural rubber composites, the relationship between the tearing energy T and the crack growth rate dc / dn was
obtained, which laid the foundation for the prediction of the fatigue life of the composites。
0 2 4 6 8 100
2
4
6
8
10
Cra
ck length
(m
m)
Cycle104
RGE 0
RGE 0.3
RGE 1.2
parabola fit
1
1
RGE 0
RGE 0.3
RGE 1.2
parabola fit
dc/d
n(m
m/1
04)
Tearing Energy(KJ/m2)
Fatigue cycle versus crack growth of the
NR/GE composites under theεmaxof 40%crack growth rate (dc/dn) versus tearing energy
of the NR/GE under theεmax of 40%
εmax=40%,Adding GE slows the crack propagation rate of the material. With the increase of GE content, the smaller the crack growth rate, the better the
growth resistance of the crack
Study on Dynamic Tensile Fatigue Properties of Graphene / Natural Rubber Composites
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CCD
Equipment of hard X-ray micro-focus beamline.
Experimental setup of X-ray diffraction for NR and GE/NRsamples with a precutcrack.
Determination for strain induced crystallization at crack tips.
Study on Dynamic Tensile Fatigue Properties of Graphene / Natural Rubber Composites
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(a) Contour maps of the
crack tip for blank NR and
GE/NR composite at
various stretch strains (b)
Crystallinity χ of NR and
GE/NR composite near the
crack tip as a function of
the distance r along the
crack propagation direction
for various stretch strains.
(c) Lateral crystallite size
(L200) versus r along Y axis
for the samples NR and
GE/NR at various stretch
strains.
GE / NR crack tip strain induced crystallization
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Applications – overview
defense tireSeal/
Isolator/….
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SSBR + Silica + GE
Rolling Resistance decrease 8%
road test reveal adding about 0.5% GE in tread result in
Breaking distance shorter about 2 meters
Applications – green tire (tread )
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Tian L, Wang Y, Li Z, et al.Drag reduction performance and mechanism ofa thermally conductive elastic wall in internalflowApplied Thermal Engineering, 2017, 123, 1152
Applications – vibration isolator
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Underwater absorption coefficients of neat rubber sample and graphene/SBR
nanocomposites
6-30 kHz range under normal pressure
0.1-5.5 kHz under different water pressure.
GE content: 8.36 vol%Nanoscale 2017
Applications – sonic absorption
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Wei J, Jacob S, Qiu J. Graphene oxide-integrated high-temperature durable fluoroelastomer for petroleum oil sealing. Composites Science and Technology, 2014, 92: 126
Applications – seal
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Applications – sensor (wearable)
• For wearable devices, monitors blood pressure, pulse, critical movement, and
breathing.
• Used to develop high-sensitivity airbags, medical equipment to monitor body
movements, as an early warning system for sudden infant death and adult sleep
apnea, as well as rehabilitation treatments that are embedded in clothing to
monitor athlete movements or illnesses.
Boland C S, Khan U, Backes C, et al. Sensitive, high-strain, high-rate bodily motion sensors based on graphene–rubber composites[J]. ACS nano, 2014, 8(9): 8819-8830.
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• First pre-dispersed composite supplier in China.
• Leading dispersing technology in the world.
• 20 ton capacity production line and expanding
• Patents in GE rubber applications
Company Brief
go with
graphene
innovation for better Chengdu Trustwell New Material Co., Ltd. www.trustwell.com.cn
Headquarter2801B Maoye Center Tower, No. 28, Tianfu Ave. North, Chengdu, 610017 [email protected] I Tel: +86 28 85190858 I Fax: +86 28 85191160
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