go graphenewith - trustwell · 2018-02-13 · 300% stress (mpa) tearstrength (n/mm) nature rubber...

innovation for better

go with

graphene


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.


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?


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?


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?


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?


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


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.


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


Process Ready

≤ 3 layer atom

thickness

Isolated network

What makes outstanding?

3

uneven disperse


Process Ready


difficult handling

almost no weight

Easy disperse in matrix

rubber like

condition

uniform disperse master batch

1/3



100x strong

than steel

Super conductor

2 D material

2/3≤ 3 layer

atom thickness



GE isolation network and latex particles relationship under lens GE flake in NR latex under lens


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



Latex mix, in situ reduce Twin roller mixing

Graphene dispersion in NR after shearing



Higher content of GE

5.15 vol% GE



Isolated network forming


thermal conductive

gas barrier

electrical conductive

3/3


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


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


competitor

TRUSTWELL



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


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


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.


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.


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?


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


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


(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


Applications – overview

defense tireSeal/

Isolator/….


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 )


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


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


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


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.


• 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

Thanks

go graphenewith - trustwell · 2018-02-13 · 300% stress (mpa) tearstrength (n/mm) nature rubber...

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