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การแปรรูปและการเสริมแรงของสารตัวเติมในยางธรรมชาติ
Utilization of Low Molecular Weight Natural Rubber and Functionalized Liquid Natural
Rubber to Improve Processing Property and Reinforcement in Filled NR Compounds
Prachid Saramolee
5320330106
1. Thesis Title
(Thai) การใช้ยางธรรมชาติน้ําหนักโมเลกุลต่ําและยางธรรมชาติเหลวที่มีหมู่ฟังก์ชันปรับปรุงสมบัติ
การแปรรูปและการเสริมแรงของสารตัวเติมในยางธรรมชาติ
(English) Utilization of Low Molecular Weight Natural Rubber and Functionalized
Liquid Natural Rubber to Improve Processing Property and Reinforcement
in Filled NR Compounds
3. Researchers
3.1 Student’s Name Mr.Prachid Saramolee ID 5320330106
3.2 Thesis Advisors’ Names
Asst. Prof. Dr. Kannika Sahakaro Advisor
Asst. Prof. Dr. Natinee Lopattananon Co-advisor
Prof. Dr. Jacques W.M. Noordermeer Co-advisor
rubber matrix leading to the reduction of vulcanizate mechanical properties. For general
products, amines or alcohols are used to reduce the polarity and increase the
hydrophobicity of silica surface resulting in good dispersion within the rubber matrix
(Jesionowski and Krysztafkiewicz, 2001). For high performance products such as tires,
coupling agents are used to bridge the polymer to silica, in which the process has to be
controlled the conditions and step of mixing in order to allow functional groups on silane to
fully react with silanol groups on silica surface during mixing stage (Luginsland et al., 2002;
Ansarifar et al., 2003; Reuvekamp et al., 2009). Furthermore, high filler loading in the
compound requires a use of processing oil to control compound viscosity and flow
properties during processing stage.
This research focuses on the effect of low molecular weight natural rubber (LMWNR)
or liquid natural rubber (LNR) and functionalized liquid natural rubber (FLNR) on processing
properties and the reinforcement in filled NR compounds. The use of LNR or FLNR is
expected to enhance flow properties and compatibility between rubber and filler. The LNR
will be modified to have epoxide groups as the main functional group which will also be
later extended to other types of functionalized low molecular weight natural rubber. Effects
of different molecular weight and amount of LMWNR as well as modification levels of
modified LNR on cure characteristic, processing properties, mechanical and dynamic
mechanical properties of filled NR compound will be investigated. Moreover, the effect of
LMWNR and/or FLNR will be compared to that of conventional silane coupling agent in
silica-filled compounds.
5. Objectives of Research
5.1 To prepare low molecular weight natural rubber or liquid natural rubber with
various levels of molecular weight and analyze for their characteristics and
properties
5.2 To modify liquid natural rubber by creating functional groups attached onto the
main chains such as epoxidized liquid natural rubber (ELNR) and graft copolymer
of LNR with vinyl monomers
5.3 To investigate the effect of molecular weights and amounts of LNR on processing
and vulcanizate properties of unfilled NR compounds
4
5.4 To investigate the influence of unmodified LNR and modified LNRs, when they
are used as compatibilizer in carbon black and silica-filled NR compounds, on the
compound and vulcanizate properties
5.5 To compare the effect of modified LNRs with conventional silane coupling agent
on compound and vulcanizate properties of silica-filled compounds
6. Expected Advantages
The reinforcing fillers have been widely developed for tire compounds, especially
the use of silica with silane coupling agent. This is in order to meet many requirements in
tire industry, especially for environmental saving, energy reduction and chemical toxicity
minimization. The use of natural-based products such as LMWNR and/or modified LNR to
improve processing properties and increase filler-rubber interaction in carbon black- and
silica-filled compounds will encourage more use of NR and develop more environmental
friendly products. This research will provide the knowledge of relationships between
molecular weight, types and functionality of modified LNRs and filler-rubber interaction
which influence on compound and vulcanizate properties of filled NR compounds.
7. Literature Review
7.1 Low molecular weight natural rubber
Natural rubber is an unsaturated hydrocarbon consisting solely of carbon and
hydrogen atom with an empirical formula of C5H8. Isoprene is a repeating unit of natural
rubber in which one double bond unit exists for each C5H8 group. NR latex is the form in
which rubber is exuded from the Hevea brasiliensis tree as an aqueous emulsion. The size
of rubber particles is in a range from about 50 oA to about 30,000 oA (3 μm). The molecular
weight (Mw) is normally in the range of 104-107g/mol (Subramanium, 1980), depending on
the age of the rubber tree, weather, method of rubber isolation and other factors. The
polydispersity of molecular weight is usually in the region of 2.5-10 (Eng and Ong, 2001).
Furthermore, NR is a long chain molecule with terminal groups that are able to form branch
points by hydrogen bonding with proteins and/or phospholipids (Morton, 1987; Tanaka,
2001; Amnuaypornsri et al., 2010). During storage, the hardness of NR will increase and this
will be in accordance with increasing value of Mooney viscosity. The higher value of Mooney
viscosity will give the better resistance of that rubber to deformation. The advantages of NR
are outstanding flexibility, excellent heat built up properties and high mechanical strength.
5
reaction temperature is high so that not only decomposition but also crosslinking or
recombination inevitably occurs. This makes it difficult to control the molecular weight
distribution. Cataldo (1998) prepared liquid polyisoprene by thermal depolymerization at
300–380°C. The pyrolysis of natural and synthetic cis-1,4-polyisoprene produces mainly
dipentene with small amounts of isoprene (2-5%).
Photolysis is a method for breaking the molecular chains with light energy such as
solar radiation, ultraviolet or visible light. Chain breaker compounds such as nitrobenzene,
hydrogen peroxide or photosensitisers are used together in degradation process, so called
photochemical methods. However, it is difficult to control the molecular weight or
molecular weight distribution. Moreover, isomerization reaction tends to proceed from a cis-
1,4-structure to a trans-1,4-structure.
With regard to chemical decomposition, the controlled degradation of NR involves
photochemical degradation, ozone cleavage, metathesis degradation and oxidative
degradation. Cunneen (1973) prepared LNR by irradiation with ultraviolet light in a presence
of nitrobenzene as a photosensitizer to give LNR having Mn of about 3,000 g/mol. Ravindran
et al. (1986, 1988) prepared LNR via photochemical degradation from NR using hydrogen
peroxide and light energy from both medium pressure mercury vapor lamp and sunlight.
LNR bearing hydroxyl end groups were obtained and the side products of around 10% were
observed such as carbonyl and carboxylic compounds. Solanky et al. (2005) studied cis-1,4-
polyisoprene degradation using first and second generation Grubbs catalysts to achieve end
functionalized acetoxy oligomers in both an organic solvent and a latex state at room
temperature. Moreover, the use of a sodium tungstate/acetic acid/hydrogen peroxide as a
catalyst to prepare LNR was studied (Zhang et al., 2010).
The method of ozone degradation has been applied only for a research purpose and
so far has no industrial value, because the reaction should be conducted at low
temperature and treatment of a large amount of ozonide is dangerous. Montaudo et al.
(1992) reported that ozonolysis reaction of cis-1,4-polyisoprene in hexane at ice bath
temperature without further treatment with either oxidizing or reducing agents led to the
formation of LNR bearing only ketone and carboxylic acid end groups. Nor and Ebdon (2000)
studied ozonolysis of NR in diluted chloroform solution at 0oC. They found that the number
average molecular weight of less than 900 g/mol was obtained after 20 min of ozonolysis.
However, the methods mentioned above are limited either because of difficulty in control
of reaction, highly toxic, or contaminant in LNR. Thus, oxidative degradation or redox system
7
is preferred. This method can cleave polymer chains with the concomitant introduction of
reactive terminal groups on the resulting oligomers. The oxidizing agents such as an organic
peroxide, hydrogen peroxide, atmospheric oxygen or ferric chloride-oxygen, coupled with a
reducing agent such as an aromatic hydrazine or sulfanilic acid were employed to
depolymerize NR to yield LNR (Pautra and Marteau, 1974, 1976). In the early days, the liquid
NR was prepared by redox system of phenylhydrazine/O2. The reactive functional end
groups such as phenylhydrazone and carbonyl were obtained and molecular weights, Mn,
were between 3,000 and 35,000 g/mol and the polydispersities were between 1.70 and 1.97
(Derouet et al., 1990; Brosse et al., 1981; Phinyocheep and Duangthong, 2000). However,
phenylhydrazine is toxic and may cause cancers. Mauler et al. (1995) investigated the chain
cleavage of styrene butadiene rubber (SBR) by using periodic acid (H5IO6) and/or ultrasonic
radiation. They showed that the degradation of SBR by H5IO6 can induce degradation of SBR
from Mw of 325,000 to 80,000 g/mol. Later, Mauler et al. (1997) studied the chain cleavage
of natural rubber by using periodic acid (H5IO6) in various solvents (2/10 v/v) and reaction
temperatures. They found that, at low temperature, the chain degradation using H5IO6 was
better in chloroform than in toluene and n-hexane. Reyx and Campistron (1997) used H5IO6
to prepare LNR from epoxidised natural rubber (ENR). They found the decrease of
epoxidised unit content from 25% in the starting rubber to 8% in the resulting degraded
rubber. 1H-NMR spectrum revealed the presence of aldehyde and methylketone at the chain
ends, residual oxiranes, secondary furanic and cyclic structures. Ritoit-Gillier et al. (2003)
studied the chain degradation of polyisoprene (IR) and epoxidised polyisoprene (EIR) using
H5IO6 in tetrahydrofuran (THF). Both final products contained aldehyde and ketone terminal
ends. Tanaka et al. (1996) proposed the process for depolymerizing natural rubber by adding
a carbonyl compound to NR latex or deproteinized natural rubber (DPNR) latex, and then
subjecting the resulting NR or DPNR to air oxidation in the presence of a radical forming
agent. Tangpakdee et al. (1998) prepared LNR by oxidative degradation using 1 phr of
potassium persulfate (K2S2O8, initiator) and 15 phr of propanal (encapsulator) at 60oC.
Phetphaisit and Phinyocheep (2003) also used 1 phr of K2S2O8 together with 32 phr of
propanal and the reaction mixture was stirred at 400 rpm at 60-80oC over 30 h. The
mechanism was proposed as shown in Scheme 1. Moreover, the intensity of
depolymerization and the extent of the chain scission reaction depend on temperature,
reaction time and concentration of the degradation agent (Okieimen and Akinlabi, 2001; Isa
et al., 2007). Okwu and Akinlabi (2007) studied the effect of Funtumia latex, which is low
8
molecular weight NR from wild rubber in Africa, blended with NR latex and compared to the
low molecular weight NR depolymerized by using nitrobenzene as a molecular weight
depressant at various reaction time. They found that the use of 27.9 wt.% of Funtumia
rubber in a Funtumia/NR blend reduced the molecular weight of NR from 7.02 x 105 to 3.12
x 105 g/mol. This was at the same level with the low molecular weight NR obtained from
the reaction of NR with nitrobenzene (1–2 wt.% of the DRC of the latex) over a period of 10
h.
Scheme 1 The mechanism of oxidative degraded reaction of DPNR in the presence of K2S2O8
and propanal (Tangpakdee et al., 1998).
phase using performic acid generated in situ by the reaction of hydrogen peroxide and
formic acid before oxidative degradation of ENR by using periodic acid at 30oC for 24 h.
Moreover, Phinyocheep and Duangthong (2000) studied the addition of acrylic acid onto
liquid epoxidized natural rubber (LENR) molecules by reacting LENR with acrylic acid at 60
and 80oC in toluene for 5 h without adding any catalyst.
Modifications of NR by grafting reaction are commonly done by emulsion
polymerization process. NR-g-PMMA can be prepared by using bipolar redox initiator system
such as cumene hydroperoxide (CHP) and tetraethylene pentamine (TEPA) in NR latex. It was
found that the increase of molar ratios of MMA to NR resulted in the increase of glass
transition temperature (Tg) and decomposition temperature (Td). The quantities of grafted
polymer on NR molecules are affected by various parameters such as monomer and initiator
concentrations, reaction time and reaction temperature (Nakason et al., 2003; Nakason et
al., 2006; Kalkornsurapranee et al., 2009). Oliveira et al. (2005) investigated the grafting
efficiency of dimethylaminoethylmethacrylate (DMAEMA) grafted onto NR. The results from
1
H-NMR spectroscopy showed no detectable grafting between NR and DMAEMA when 10
wt% of DMAEMA were used, but the amount of grafting increased to a significant amount
when NR was grafted with 30 wt% of DMAEMA. Derouet et al. (1990) studied the
modifications of NR with maleic anhydride. The obtained product was subsequently reacted
with photo-reactive alcohols such as 2-hydroxyethyl acrylate (HEA) and 2-hydroxyethyl
cinnamate (HEC) to give ultraviolet curable telechelic natural rubber (TLNR). Nakason et al.
(2004) studied the grafting of maleic anhydride (MA) onto NR in a toluene solution. It was
found that quantities of the grafted MA on NR molecules increased with increasing monomer
and initiator concentrations. An increase of reaction time and reaction temperature also
caused the increasing level of grafted MA.
7.3 Rubber processability improvement
An application of processing aids or plasticizers in rubber compounds are driven by
expectation to improve some original properties of rubbers and products such as to
decrease the glass transition temperature of the polymer, to make the material more
flexible, to increase elongation and decrease tensile strength, to improve its impact
resistance and to control viscosity. Plasticizers are low viscosity liquids, which reduce
viscosity of polymer and improve processability of complex industrial formulations. Addition
of low molecular weight plasticizers improves processing properties but may induce some
11
problems arising by their migration or volatilization. The reactive plasticizers which can
chemically react with polymer will eliminate those afore mentioned problems.
LNR can be used as viscosity modifier, tackifier, and plasticizer to improve the
processability of rubbers used in tire compounds (Hashim et al., 2002). The utilization of
LMWNR blended with the high molecular weight natural rubber (HMWNR) in filled rubber
compound will enhance processability and other properties due to LMWNR is able to
penetrate between the chains of HMWNR. Okieimen and Akinlabi (2002) investigated the
processing characteristics and physic-mechanical properties of NR modified with LNR of
varying molecular weights. The decrease of Mw of LNR used in the blend of NR/LNR (70/30
wt/wt) resulted in better solubility in solvents, lower initial plasticity and Mooney viscosity,
lower maximum torque and crosslink density, and lower modulus and tensile strength.
Furthermore, the LNR was used as a plasticizer in nitrile rubber compared with dibutyl
phthalate (DBP) (Nair et al., 1997; Mounir et al., 2004). Hydroxylated liquid natural rubber
(HLNR) of different proportions was mixed with epoxy resin (Mathew et al., 2010).
Furthermore, Dahlan (2000) and Dahlan et al. (2002) investigated the used of LNR as a
compatibilizer in NR/LLDPE binary blends. The addition of low Mw (in a range of 9.25 x 104)
LNR reduced the interfacial tension, therefore improved the interactions between the
phases in the blends, while high Mw (in a range of 4.80 x 105) LNR showed some plasticizing
effect to the blends. Epoxidised LNR (ELNR) had been used as plasticizer or processing aid
during processing of some polymers, such as NR/acrylonitrile butadiene rubber (NBR) blend
(Wonkam et al., 2000) and PVC/ENR blend (Nair et al., 2007; Biju et al., 2007; Nair et al.,
2009). In addition, ELNR could enhance the compatibility in the blend of liquid
deproteinized natural rubber having epoxy group (LEDPNR) with poly(L-lactide) (PLLA) (Nghia
et al., 2008). It was observed that an increase in mol percent epoxidation of the liquid
rubber enhanced compatibility and the lower molecular weight epoxidized rubber yielded
better property modifications than the higher molecular weight rubber.
7.4 Rubber-filler interaction improvement
A wide variety of particulate fillers are used in the rubber industry to improve the
physical and mechanical properties of elastomeric materials. The addition of filler usually
leads to an increase of modulus, whereas significant improvements in tensile and tear
strength, and wear resistance will depend on type and amount of filler used. Filler
morphology such as particle size and structure as well as specific surface activity has a large
influence on the physical properties of the elastomeric material (Bokobza and Rapoport,
12
2001). The mechanism of rubber reinforcement involves an adsorption of the network chains
onto the particle surfaces resulting from either physical interactions, e.g. Van der Waals
forces between the filler surface and the polymer, or chemical interaction or both. These
characteristics contribute to the reinforcement of the elastomers through interactions
between elastomers and fillers (Wolff and Wang, 1994). Silica filler has become more
important in tire applications since the introduction of the “Green Tire” by Michelin
(Rouline, 1992). Silica has some greater reinforcing performance such as tear strength, heat
resistance and adhesion properties compared to carbon black. However, due to the strong
interparticle hydrogen bonds between hydroxyl groups, silica is generally in the form of
agglomerates which will be broken down into aggregates during mixing or under certain level
of dynamic deformation. Compared to reinforcing carbon black, silica retards the sulfur
vulcanization reaction of the filled compounds, which is attributed to the adsorption of
curatives on the silica surface and acidic nature of silica. Furthermore, the silanol content,
adsorbed water content and surface area of the silica also affect the cure time (Wolff et al.,
1993; Wagner, 1976). The addition of glycols, amines or guanidines such as diethylene glycol
or triethanolamine in silica-filled compounds can reduce the Mooney viscosity and scorch
time.
The strategies to improve silica- rubber interaction and reduce the rolling resistance
are, for examples, a use of coupling agent, chemical modifications of rubbers by attaching
functional groups which can interact with silica, and modification of silica surface. Silane
coupling agent is used to chemically bind the polymer to silica, thus increasing the level of
reinforcement. However, silane coupling agent voids some disadvantages such as high cost,
toxicity, risk of precuring during the mixing stage and the generation of ethanol during mixing
so that limit its widespread use (Wolff, 1996). The interaction between the silica surface and
the polar groups of the elastomer should make it possible to omit a silane coupling agent
out of compound formulations (Choi, 2001; Suzuki et al., 2005). The nitrile groups (-CN) of
acrylonitrile butadiene rubber (NBR) are expected to form hydrogen bond with silica in the
silica-filled NBR compound. In addition, it has been reported that the properties of silica-
filled natural rubber (NR) compounds were improved by using chloroprene rubber (CR) (Choi,
2002). The increasing of bound rubber content of the compound and physical properties
were attributed to the good dispersion of silica by adding CR. Dileep and Avirah (2003)
prepared carboxy-terminated liquid natural rubber (CTNR) by a photochemical reaction and
was then applied as a potential modifier in filled NR vulcanizates. It was found that CTNR
13
could improve the tensile properties, ageing and oil resistance of NR vulcanizates due to the
improvement of the rubber-filler interaction in NR vulcanizates. Furthermore, it could also
act as a polymeric plasticizer in filled NR vulcanizates. Choi et al. (2003) improved filler
dispersion of the silica-filled SBR compound by adding the liquid polybutadiene (PBD). The
faster cure time and cure rate were observed when the 1,2-unit content of the liquid PBD
was increased. In addition, crosslink density, modulus and tensile strength increased with
increasing the 1,2-unit content.
Varkey et al. (1998) indicated that a small proportion of ENR could be used as an
interface modifier for NR-silica systems and as a reinforcement modifier for silica-filled NBR.
Incorporation of an optimum concentration of about 15% of ENR on total rubber in silica-
filled NBR compound was found to improve bound rubber, mechanical and dynamic
mechanical properties (George et al., 2002, 2006). As shown in Scheme 2, it was postulated
that the ENR could react with the silanol group of the silica surface and the double bond of
ENR underwent crosslinking by reacting with sulfur added in the compound during
vulcanization (Manna et al., 1998, 1999, 2002; Cataldo, 2002; Xu et al., 2007). ENR with up to
50 mole % epoxide had been used alone and in combination with other diene rubbers such
as NR, SBR or BR at a level of ENR higher than 30 phr with precipitated silica and a mixture
of silica with carbon black to improve wet skid resistance, however, poor tire tread abrasion
and tear properties were observed (Nasir et al., 1989; Varughese and Tripathy, 1992). As
shown in Figure 1, it was demonstrated that tire treads made from silica-filled ENR-25 had
both lower rolling resistance and better wet grip when compared to the carbon black-filled
NR or SBR tread compounds (Baker et al., 1985; Chapman, 2007).
14
Scheme 2 The mechanism of bonding between ENR and precipitated silica (Manna et al.,
1999).
Figure 1 Relation between wet grip and rolling resistance of retreaded passenger car tyres
(Chapman, 2007).
Furthermore, epoxidized rubber seed oils have been reported to enhance the
adhesion properties of rubber with silica, as indicated by the better physical and mechanical
properties (Joseph et al., 2004). The use of diamine salt of fatty acid in silica-filled NR and
ENR could improve silica dispersion, mechanical properties and also crosslink density (Ismail
and Chia, 1998). In addition, maleated natural rubbers (MNRs) can be used as a
compatibilizer in silica-filled NR compounds. The MNR with 6 phr of maleic anhydride
showed the lowest filler-filler interaction and optimum mechanical and dynamic mechanical
15
properties due to succinic anhydride groups grafted onto natural rubber molecules of the
MNRs could interact with hydroxyl groups on silica surface (Sahakaro and Beraheng, 2008).
9. Research Methodology
9.1 Materials and Instruments
9.1.1 Materials
- Ribbed smoked sheet (RSS)#3 natural rubber
- High ammonia concentrated latex
- Potassium persulfate
- Propanal
- Sodium hydrogen phosphate
- Teric N-30
- Formic acid
- Hydrogen peroxide
- Methyl methacrylate
16
- Cumene hydroperoxide
- Tetraethylenepentamine
- Silica
- Bis-(3-triethoxysilylpropyl) tetrasulfide
- Zinc oxide
- Stearic acid
- Diphenyl guanidine
- N-cyclohexyl-2-benzothiazyl sulfenamide
- Sulfur
- Treated distillate aromatic extract (TDAE) oil
- Solvents, e.g., toluene methanol, acetone and chloroform
9.1.2 Instruments
- Internal mixer
- Two roll mills
- Compression molding machine
- Ubbelhode viscometer
- Gel permeation chromatograph (GPC)
- Fourier transform infrared spectrometer (FT-IR)
- Proton nuclear magnetic resonance spectrometer (1H NMR)
- Capillary rheometer
- Moving die processability tester (MDPT)
- Oscillating disk rheometer (ODR)
- Mooney viscometer
- Tensile testing machine
- Scanning electron microscope (SEM)
- Dynamic mechanical analyzer (DMA)
9.2 Experiment
Part I: Preparation and characterization of low molecular weight natural rubbers
Low molecular weight natural rubber (LMWNR) or liquid natural rubber (LNR) will
be prepared by oxidative degradation method in latex state (20%DRC of high ammonia-
concentrated NR latex) using 1 phr of potassium persulfate (initiator) with 15 and 30 phr of
17
propanal (encapsulator) (Tangpakdee et al., 1998). The rubber latex will be sampled at
various reaction times and coagulated in acetone. After coagulation, the LNR will be
reprecipitated from toluene using methanol, washed thoroughly with water and dried in a
vacuum at 40°C. The obtained LNR are to be characterized by GPC and Ubbelhode
viscometer for molecular weight and FT-IR for structure. Mooney viscosity and other physical
properties (e.g. Po, PRI and color) will be also investigated. The conditions for oxidative
degradation will be optimized to obtain LMWNRs with Mw in a range of 5,000-100,000 g/mol.
properties (by using capillary rheometer) and mechanical properties such as hardness,
modulus, tensile strength and elongation at break will be investigated.
Table 1 Formulation of gum rubber compounds.
Part IV: Influence of LNR and FLNR on processing and vulcanizate properties of
carbon black-filled compounds.
The influence of low molecular weight natural rubber and functionalized liquid
natural rubber such as ELNR and LNR-g-PMMA in carbon black filled compounds will be
investigated in this part. The compound formulation is as shown in Table 2. Optimization of
the mixing conditions such as compound dump temperatures and filler-rubber mixing step
will be performed. Molecular weights, amounts and functionalized degrees of LNR and
modified LNR will be subjected to study for their influence on the carbon black filled
compounds. Properties of the filled compounds under investigations are processing
properties such as Mooney viscosity, shear viscosity and mixing energy; filler-rubber and
filler-filler interactions such as bound rubber, Payne effect; and cure characteristics such as
minimum and maximum torque, scorch time, cure time and cure rate index. Moreover,
mechanical and dynamic properties such as hardness, modulus, tensile strength, elongation
at break, tear strength, abrasion resistance, storage modulus, loss modulus and tan δ will be
investigated. Filler dispersion will be investigated by using Scanning Electron Microscope
(SEM).
19
11. Places
- Department of Rubber Technology and Polymer Science, Faculty of Science and
Technology, Prince of Songkla University, Pattani Campus, Thailand.
- Wood Science and Engineering Research Unit, School of Engineering and Resources
Management, Walailak University, Nakhon Si Thammarat, Thailand.
- Department of Elastomer Technology and Engineering, Faculty of Engineering
Technology, University of Twente, the Netherlands.
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Prachid Saramolee
(Mr.Prachid Saramolee) Student
Date 15/08/2011
Kannika Sahakaro
(Asst. Prof. Dr. Kannika Sahakaro) Advisor
Date 15/08/2011
Natinee Lopattananon
(Asst. Prof. Dr. Natinee Lopattananon) Co-Advisor
Date 15/08/2011