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Characterization of Amazonic WhitePitch (Protium heptaphyllum) forpotential use as ‘green’ adhesiveRaimundo Kennedy Vieiraa, Adalena Kennedy Vieirab, Jun Tae Kimc

& Anil Narayan Netravalida Faculty of Technology, Federal University of Amazonas, Manaus,AM 69077-000, Brazilb Chemistry Department, Federal University of Viçosa, Viçosa, MG36571-000, Brazilc Department of Food Science & Technology, Keimyung University,Daegu 704-701, Koread Department of Fiber Science & Apparel Design, CornellUniversity, Ithaca, NY 14853-4401, USAPublished online: 28 Jan 2014.

To cite this article: Raimundo Kennedy Vieira, Adalena Kennedy Vieira, Jun Tae Kim & AnilNarayan Netravali (2014) Characterization of Amazonic White Pitch (Protium heptaphyllum) forpotential use as ‘green’ adhesive, Journal of Adhesion Science and Technology, 28:10, 963-974,DOI: 10.1080/01694243.2014.880220

To link to this article: http://dx.doi.org/10.1080/01694243.2014.880220

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Characterization of Amazonic White Pitch (Protium heptaphyllum)for potential use as ‘green’ adhesive

Raimundo Kennedy Vieiraa*, Adalena Kennedy Vieirab, Jun Tae Kimc andAnil Narayan Netravalid

aFaculty of Technology, Federal University of Amazonas, Manaus, AM 69077-000, Brazil;bChemistry Department, Federal University of Viçosa, Viçosa, MG 36571-000, Brazil;

cDepartment of Food Science & Technology, Keimyung University, Daegu 704-701, Korea;dDepartment of Fiber Science & Apparel Design, Cornell University, Ithaca,

NY 14853-4401, USA

(Received 30 June 2013; final version received 23 December 2013; accepted 30 December 2013)

The plant species Protium heptaphyllum, widely found in the Amazon and northeastregions of Brazil, produces an oily resin commonly known as White Pitch (BreuBranco) (WP). The WP has been shown to have the characteristics to produce a sortof ‘green’ polymer. The aim of this study was to characterize commercially avail-able WP resin for its chemical and mechanical properties and to assess its suitabilityfor use as green adhesive. The WP obtained from typical Amazon market was puri-fied and characterized for its chemical nature using GC/MS, TGA, DSC, and FTIR.The results also confirmed that the material used was indeed from P. heptaphyllumplant species. The mechanical and thermal properties were characterized, and itsadhesion was measured. Adhesive shear and tensile strength of the WP bondedwood specimens were investigated using a small scale test method. The shearstrength of the WP bonded wood specimens was always higher than the tensilestrength, but this value was lower when compared with commercial adhesives.

Keywords: green materials; characterization; Amazon White Pitch; bréu branco;adhesion

1. Introduction

Protium heptaphyllum, a plant species mostly found in the Amazon and northeastregions of Brazil, produces an oily resin commonly known as White Pitch (BréuBranco) (WP). The WP resin is naturally produced and exuded in the fluid form as aself-protection mechanism when the tree is injured or bitten by an animal in the forest.Various WP resin products with somewhat different chemical compositions are avail-able in the market. The different compositions of the WP are a consequence of thelocations they are obtained from and the different weather conditions, in which theplants are grown. Since the properties of WP resin depend on its chemical structureand composition, many researchers have studied and characterized WP resin constitu-ents prior to its applications.[1–4] Based on previous studies, the major component ofWP resin consists of a combination of two pentacyclic triterpenes, α- and β-amyrin. Inprevious literatures, WP has been investigated for its anti-conceptive, anti-inflammatory,antimicrobial, and antioxidant activities as well as gastro protective effect.[3–8] Beyond

*Corresponding author. Email: maneiro01@ig.com.br

© 2014 Taylor & Francis

Journal of Adhesion Science and Technology, 2014Vol. 28, No. 10, 963–974, http://dx.doi.org/10.1080/01694243.2014.880220

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these applications, WP has also been used in perfume industry because of its pleasantsmell. Since WP is insoluble in water and only partially soluble in cold alcohol, addingit to perfumes helps in extending its longevity. One of the traditional applications ofWP has been as caulking in boat building.[9] While no scientific studies on theadhesive application of WP have been carried out, its application as caulking suggeststhat WP may have great potential as an eco-friendly and fully biodegradable ‘green’adhesive. This provided the motivation for this study.

In the present study, raw WP exudate was obtained from a Brazilian local market,purified, and characterized to understand its chemical composition and physicochemicalproperties. The adhesion properties of WP resin with respect to wood were then investi-gated by measuring the adhesive shear and tensile strengths using maple wood sticks.

2. Experimental

2.1. Materials

The resinous WP exudate, in the raw form, from the trunk wood of P. heptaphyllumwas purchased from the Ver-O-Peso market in Belem, Brazil. Figure 1 shows the pic-ture of a typical raw WP exudate chunk. Maple wood strips with dimensions of 85 ×15 × 2 mm (L ×W × T) were obtained from A. C. Moore store in Ithaca, NY. Ethyl ace-tate (CH3COOCH2CH3) was purchased from Sigma Aldrich (St. Louis, MO, USA),and ultra-purified water with a specific resistance of 1MΩ cm was obtained by reverseosmosis followed by ion exchange and filtration (Milli-DI Water Purification System,EMD Millipore Corp., Billerica, MA).

2.2. Preparation of WP resin and film

WP resin was extracted from raw WP exudate by first dissolving it in ethyl acetate at70 °C and filtering it using paper filter 1 (Whatman 1001-150) with average porediameter of 11 μm. The filtrate was then dried at room temperature for 72 h prior to its

Figure 1. Picture of brute WP.

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characterization. This dried WP resin was used in all further tests. The WP resin filmswere prepared by heating the resin to 170 °C and pouring the molten resin onto aTeflon® coated glass plate and allowing it to spread into thin film. The WP resin filmwas characterized using FTIR, GC/MS, and thermal analyses. In addition, the WP resinfilm was also characterized for its hardness, Contact Angle with water, and as adhesivefor wood.

2.3. Attenuated total reflectance-Fourier transform infrared analysis

Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra of unpurifiedand purified WP samples were collected using a Nicolet Magna 560 FTIR spectrometerwith a split pea accessory for ATR. Each scan was an average of 130 scans recordedfrom 4000 to 400 cm−1 wavenumbers obtained at a resolution of 4 cm−1. All specimenswere dried prior to conducting the ATR-FTIR spectroscopy.

2.4. GC/MS analysis

A 15 mg specimen of purified WP was dissolved in 15 ml of ethyl acetate. WP resinsample was then analyzed by an Agilent 6890 N Network GC system equipped with anAgilent 5973 Network mass selective detector and Agilent 7683 series injector. TheGC/MS conditions were as follows: a 30 m × 0.25 mm (inside diameter) fused silicacapillary column with 0.25-μm film thickness (HP19091S-433, GenTech Scientific Inc.,Arcade, NY) and a carrier gas of helium (70 kPa) were used; initial temperature was150 °C for 5 min, increasing to 290 °C at 5 °C min−1, then kept for 30 min; injector porttemperature was 200 °C; detector temperature was 290 °C.

2.5. Thermal analysis

Thermogravimetric analysis (TGA; model 2050, TA Instruments Inc., New Castle, DE)was used to characterize the thermal degradation profile of the WP resin. WP resinspecimen was scanned from 30 to 400 °C at a ramp rate of 15 °C/min under nitrogenenvironment. The thermal behavior of WP resin was also characterized using a differ-ential scanning calorimeter (DSC; model 2920, TA Instruments Inc., New Castle, DE).WP specimens, 5–10 mg, were scanned from 30 to 400 °C at a scan rate of 15 °C/minunder an inert atmosphere by keeping the nitrogen flow rate of 50 ml/min.

2.6. Hardness tests

The hardness measurement was carried out using a Celestron LCD Digital OpticalMicroscope to make the optical observations according to ASTM D 3363-05.[11] TheWP resin film was prepared by heating the resin at 170 °C until it fully melted, thenpouring it onto a glass slide, and spread to desired thickness. To obtain the hardnessvalues, different calibrated hardness pencils were used to try and make some type ofdamage in the coating of WP resin film such as: to scratch or rupture it. These pencilswere used in a sequence from the softest to the hardest. The kind of pencil whichproduced some type of damage, particularly scratch, was then reported as thehardness of the material being tested. The range, from softest to hardest, was asfollows: 6B–4B–2B–HB–2H–4H–6H. This method has been used by the coatingindustry to determine the cure and hardness of clear and pigmented organic films.

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2.7. Contact angle measurement

Imass contact angle analyzer (model CAA2) was used to measure the contact angle ofWP film with distilled water drops. This test was done to determine the level of wetta-bility of the WP film. To obtain the contact angle, WP resin was heated at 170 °C untilthe resin melted and spread over a microscope glass slide to form a film of approxi-mately 1 mm thickness. A measured drop of HPLC grade distilled water was placed onthe WP film, and the contact angle was measured.

2.8. Adhesion tests

Adhesion properties in both shear and tensile modes of WP resin were investigated withmaple wood strips using an Instron (model 5566, Instron Co., Canton, MA). Test todetermine adhesive shear strength was performed according to ASTM D1002.[12] Forthis, WP resin was heated at 170 °C until the resin melted completely. Two 15 mm widemaple wood strips were placed in parallel direction with bonded area of 15 × 15 mm atthe end of the strips, and two short pieces of the same wood strip were attached to theother ends to avoid undergoing torsion in the grip during the shear test. The crossheadspeed of 1.3 mm/min was used. The maximum load at break was recorded, and theadhesive shear strength, τ, was calculated using the following equation:

s ¼ PM

L�Wð1Þ (1)

where PM is the maximum load, L and W are the bonded length and width,respectively. At least 10 specimens were tested to obtain the average values.

To obtain adhesive strength in tension mode, the top wood strip was placed in aperpendicular direction on top of the bottom wood strip as shown in Figure 2(f). The

Figure 2. Pictures of (a) commercial binder clips, (b) holder of tensile testing, and thespecimens mounted using two holders in the Instron observed from (c) front, (d) top, and (e)bottom sides, and (f) area under stress.[15]

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resin was applied at the interface (15 × 15 mm area) in between the top and bottomwood strips. Then, the specimens were hand pressed for 30 s. Immediately prior topreparing shear and tensile test specimens, the wood strips were placed in an oven at120 °C for 15 min so as to avoid thermal shock when the adhesive was poured over thestrips. For the adhesive test in tensile mode, ASTM D897 [13] or D2095 [14] are com-monly used as a standard testing method. However, these tests need special accessory,machine, or bar shape specimen. At the same time, in the present case, because theresin was brittle and unavailability of the special accessory, the adhesive test in tensilemode for the WP-based adhesive could not be performed. In an earlier study, Kim andNetravali developed a simple and small scale test method for characterizing tensileproperties of adhesives with wood strips [15] based on ASTM D-1344.[16] In thesetests, commercially available binder clips (Figure 2(a)) were modified to perform asspecimen holder as shown in Figure 2(b). The wood strip specimen could be easilymounted using two of such holders, one for the top and one for the bottom.Figure 2(c)–(e) shows the wood strip specimens mounted in the Instron observed fromfront, top, and bottom sides, respectively. Tensile strength of the adhesive-bonded woodstrips was characterized using the same Instron (model 5566) with the binderclip-modified holder. The crosshead speed was 1 mm/min and at least, 10 specimenswere tested to obtain the average adhesive tensile strength.

3. Results and discussion

3.1. GC-MS analysis

Figure 3 shows the GC-MS spectrum of the purified WP resin. The three major peaksobserved are attributed to α-amyrin, β-amyrin, and keto-ester, as marked. The detailedcomposition of WP resin is summarized in Table 1. The mixture of α- and β-amyrinwas estimated to be about 76%, based on the GCMS results. This result confirmed thatα- and β-amyrin are the most abundant and the principal components of WP resin,which confirm the authenticity of the material used in this study. This result can becompared with the previous study by Bertan that found 65.1% of α- and β-amyrin mix-ture, as showed in Table 1.[10] The proportion of α- and β-amyrin and the chemicalcompositions of WP resin, such as the presence of different types of esters or steroidacids, are expected to be different depending on the cultivated locations and the localweather conditions.[10]

3.2. ATR-FTIR analysis

ATR-FTIR analysis was used to confirm the GC/MS results and to detect any composi-tion change of WP after the purification by ethyl acetate (EtAcO). Figures 5 and 6 areshowed ATR-FTIR spectra of the unpurified WP resin and the purified WP resin,respectively. The most conspicuous changes observed were at wavenumbers 1010,1074, 1143, 1346, 2923 cm−1 and in the range from 3200 to 3500 cm−1 in Figure 4.These bands and peaks are assigned to various bonds of cellulose.[17] However, thesepeaks were mostly reduced after purification as shown in Figure 5. This indicates thatthe extraction of WP by EtAcO was able to separate the organic polar phase of thewood residual. The reduction in the peaks and bands listed above is primarily due tothe removal of cellulose. However, that is compensated by relative increase in peakassignment for EtAcO, amyrins, and keto-ester, which are related to C–O, C–C, and

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C–H bonds as illustrated in Figure 5. The emphasis must be given to the peaks at3303, 1970, and 1708 cm−1, which are assigned to O–H of the α- and β-amyrins, theabsorption of C–O, and the absorption of C–O, respectively, relative to α- and β-unsat-urated ketone.[18,19] This confirms the structure of keto-ester found in GC/MS analysisdiscussed earlier.

3.3. Thermal analysis

Figure 6 shows the typical TGA thermogram of WP resin. Initial weight loss of about9% observed below 200 °C is mainly attributed to the evaporation of water and residualsolvent (ethyl acetate). The rapid weight loss appeared between 200 and 345 °C indi-cates the steady decomposition of the major components of WP, the α-, and β-amyrinsand confirms the results of Vieira et al [20]. In the DSC thermogram for WP shown inFigure 7, four endothermic peaks were observed. The endothermic peaks at around98 °C and at 140 °C are associated with the evaporation of volatile substances such as

Figure 3. GC/MS spectrum of WP.

Table 1. Retention time and constituent percentages of the fixed fraction of White Pitch basedon relative areas of peaks corresponding to this study compared with the data from Bertan [10].

Retention time (min) Mix (%)

Present data Bertan [10] data Compounds (molecular weight) Present data Bertan [10] data

39.26 38.03 β amyrin (426) 26.02 22.040.33 39.07 α amyrin 50.04 43.1– 41.19 Steroidal acid – 10.8– 41.69 Steroidal acid – 14.1– 44.20 Steroidal acid – 9.8547.18 – Keto-ester 9.10 –

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Figure 4. FTIR spectrum of unpurified WP resin.

Figure 5. FTIR spectrum of purified WP resin.

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water and residual organic solvents, respectively, as suggested by the TGA thermogramof WP resin shown in Figure 6. The third peak at 181 °C can be attributed to meltingof the remaining components, such as of α- and β-amyrins, as explained by Olivieraet al [7]. The fourth peak at the high temperature of about 345 °C can be attributed tothe decomposition of the sample as suggested by the TGA analysis.

3.4. Contact angle measurement

Table 2 shows the static contact angle of distilled water on the WP resin surface. Asthe contact angle with water was found to be higher than 100°, the resin film can besaid to have hydrophobic characteristic. This may be beneficial when this resin is usedcommercially in composites because it will have no problems associated with hydro-philic resins such as swelling, loss of mechanical properties as well as lower durability.However, since wood is cellulosic and hydrophilic, the hydrophobic resin would not beexpected to spread on it easily.

3.5. Hardness analysis

The hardness of the WP resin was tested in triplicate at different locations. All speci-mens showed satisfactory results with respect to homogeneity of the film made withthe resin, that is, the hardness was uniform and around 4H. This value of hardness issimilar to that obtained to the polymethylmethacrylate by Kao and Hong [21]. The 4Hhardness value suggests that the scratch resistance of the resin is considered satisfactorybecause the resin is vitreous causing a good resistance to scratch.

3.6. Shear and tensile adhesion tests of WP resin

Adhesive shear and tensile strengths of WP resin with commercial maple woodspecimens are presented in Table 2. These tests were performed using the new test

Figure 6. TGA thermograph of WP resin.

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method developed by Kim and Netravali for small specimens.[15] The results showedmuch lower adhesive tensile strength than the adhesive shear strength for the WP resinand wood specimens. These results are similar in trend to those obtained by Kim andNetravali [15] as can be seen in Table 2. Also, as mentioned by Frihart [22], bondedassemblies are usually weaker in tension than in shear or compression because it iseasier to pull the chains apart.

The adhesive tensile strength of WP resin with maple wood specimens rangedbetween 0.10 and 0.18MPa, with average of 0.12MPa and the adhesive shear strengthwas only around 1.30MPa. As this test was based on ASTM D-1344, generally, this

Figure 7. DSC thermograms of WP resin.

Table 2. Properties of WP resin.

Commercial adhesives

WP resinSPCb

[14]TBIIc

[14]PEG200d Epoxy

resin [21]Bisphenol-Ae Typeepoxy resin [21]

Hardness 4H – – – –Contact angle 100.77

(15.41)a– – – –

Adhesion undertractionstresses (MPa)

0.14(42.16)

0.34 1.78 3.5 62.8

Shear adhesion(MPa)

1.45(48.23)

1.2 6.0 1.7 14.6

aFigure in parentheses is CV%.bSoy protein concentrate. Adhesive substrates were maple wood.cTitebond-II. Adhesive substrates were maple wood.dPolyethylene glycol. Adhesive substrates were steel plates.eAdhesive substrates were steel plates.

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testing, even under the best of circumstances, one would not anticipate the stressdistribution in such a case to be very uniform. The exact stress distribution is highlydependent on the relative flexibilities of both the cross-beams and the adhesive. For thisreason, a comparison with a work using the alike equipment and same wood like madeby Kim and Netravali [15] became possible for a good analysis on the behavior of theresin under study. These values for both shear and tensile strengths are lower whencompared with commercial adhesive as shown in Table 2. This could be explained bymechanical properties dependent upon the chemical structure. Knowing the chemicalstructure of the adhesive and interphase helps to understand the adhesive’s perfor-mance.[22] In the case of WP resin, in the lower performance could be a function oftwo factors. First, as mentioned earlier, the resin was hydrophobic. Maple wood beinghydrophilic, the resin is difficult to spread on the wood specimen. As a result, there isonly limited WP resin–maple wood interaction. The second reason is the high viscosityof the resin which does not allow it to penetrate deep in the maple wood specimen cre-vices, thus providing very limited mechanical bonding. The maple wood specimensused in this study were smooth and hence did not provide the resin deep crevices, aswell. Both these factors contribute to lower the adhesive performance of the WP resin.

The resin penetration into the crevices was seen to be further affected by rapid crys-tallizing of the WP resin during test specimen preparation. This issue was attempted tobe resolved by heating the resin to 170 °C. The rapid crystallization did not provideenough time for the resin penetrate easily into the wood surfaces resulting in decreasedadhesion strength. As mentioned earlier, the wood pieces were also heated to 120 °C toslow the resin crystallization. However, both actions did not solve the problem.

As discussed earlier, the chemical structure of WP resin shows the presence of threeprincipal organic components. The α- and β-amyrins are aromatic alcohols whichincreases the possibility interaction with the hydrophilic surface of wood (cellulose)through hydrogen bonding. In addition, there is the possibility of aromatic rings of α-and β-amyrins as well as keto-ester interacting with aromatic compounds of the lignin.Thus, the fact of WP resin to be extracted from wood raises the possibility of someinteraction when applied used as wood adhesive. While it seemed reasonable to achievegood adhesion, the other factors discussed earlier, overall hydrophobicity as a result ofthe overall aromatic nature, high viscosity of the WP resin, and rapid crystallization,seem to limit the bonding. In summary, while the present studies did not show WPresin to be satisfactory for adhesively bonding wood, it is already being used as a goodadhesive by the people living in the Amazon Region in Brazil. This suggests that morestudies are needed to understand and enhance the properties of the WP resin.

4. Conclusions

In this study, the presence of α- and β-amyrins in WP resin was confirmed throughGC/MS analysis. The results also confirmed that the material used was indeed from P.heptaphyllum plant species. The FTIR analysis indicated that ethyl acetate can be usedto separate cellulosic material from the WP resin and, moreover, it can provide quickand inexpensive way to identify the White Pitch.

The TGA thermogram for WP resin showed two-step mass loss, the first minor stepwas attributed to evaporation of water and waste organic solvents and the second stepwas attributed to the degradation of the resin itself. The DSC thermogram of the resinsample showed endothermic event characteristic of evaporation and thermaldecomposition of adsorbed substances, as indicated in the TG curve.

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Adhesive shear and tensile strength of the WP bonded wood specimens wereinvestigated using a small scale test methods. The shear strength of the White Pitchbonded wood specimens was always higher than the tensile strength, but this value wasfar lower when compared with commercial adhesives.

More studies are needed to understand and improve the properties of WP resin,which due to medical properties could be used in composite bandage both with thefunction of binder such as antimicrobial.

AcknowledgementsThe authors would like to thank Cornell Center for Materials Research (CCMR) and theDepartment of Fiber Science & Apparel Design for the use of the facilities. AKV and RKV thankthe CAPES (Brazil) for the fellowships and for the PRO-ENGENHARIA program.

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