recycled wastepaper · bleached wood preparation and … · 2019-05-21 · m.e. abd el-aziz, essam...

ROHSTOFFE UND ANWENDUNGEN RAW MATERIALS AND APPLICATIONS

36 KGK · 04 2019 www.kgk-rubberpoint.de

Recycled wastepaper · bleached wood pulp · CMC · HA-NPs · heavy metals removal

The paper sheets nanocomposite of cel-lulose pulp/ carboxymethyl cellulose/ hydroxyapatite nanoparticles (HA-NP) were prepared with different ratios of HA-NPs. Two types of cellulose pulps were used, the recycled wastepaper pulp (RWP) and the bleached wood pulp (BWP) to prepare RWP/CMC/HA-NPs and BWP/CMC/HA-NPs, respectively. The characterizations of HA-NPs and the pa-per sheets nanocomposite as well as their affect in the removal of Fe2+, Cu+2 and Cd2+ ions were studied. It was found that the swelling % decreased by in-creasing the HA-NPs content in the pa-per sheets. Also, the mechanical proper-ties of the paper sheets nanocomposite obtained from BWP were higher than that obtained from RWP. In addition, the ratio of removal heavy metal ions was increased by increasing the ratio of HA-NPs in the paper sheets nanocomposite.

Herstellung und Charakterisie-rung von CMC/HA-NPs/Zell-stoff-Nanokomposite für die Entfernung von Schwermetall-ionen Recycling-Altpapier · gebleichter Zell-stoff · CMC · HA-NPs · Schwermetall- entfernung

Es wurde Papier aus Zellstoff/Carboxy-methylcellulose/Hydroxylapatit-Nanop-artikeln (HA-NP) mit unterschiedlichen Verhältnissen von HA-NP hergestellt. Da-bei wurden zwei Arten von Zellstoff zur Herstellung von RWP/CMC/HA-NPs bzw. BWP/CMC/HA-NPs verwendet, der Alt-papier Zellstoff (RWP) und der gebleichte Zellstoff (BWP). Der Effekt von herge-stellten Papier-Nanokomposite auf die Entfernung von Fe2+, Cu+2 und Cd2+ Ionen wurde untersucht. Darüber hinaus wur-de das Quellen der Papier-Nanokomposi-te in wässrigen Lösungen untersucht. Die Erhöhung des HA-NPs-Gehalts im Papier bewirkt eine Abnahme der Quel-lung. Die mechanischen Eigenschaften der aus BWP erhaltenen Papier-Nano-komposite waren besser als die von RWP.

Figures and Tables: By a kind approval of the authors.

IntroductionA paper sheet is formed from a network structure between cellulosic and non-cellulosic materials (hemicelluloses and lignin), where it is connected together via hydrogen bonds [1,2]. The mechani-cal properties of the paper sheet can be enhancement by increasing the crossing between the cellulosic fibers. There are different materials such as cellulose ace-tate [3], carboxymethyl cellulose [4], cationic polyacrylamides, cationic starch [5] and polyvinyl alcohol [6] which in-creasing the interfiber bonding between the cellulose chains in the formed paper sheets. These materials enable the interfiber bonding areas to remain chemically linked in the presence of wa-ter. Another way to reinforce the proper-ties of paper sheet can be achieved by a chemical modification on the cellulose fiber, such as acetylation [6], carboxym-ethylation and grafting [7].

Carboxymethyl cellulose (CMC) is an anionic polyelectrolyte obtained from cellulose. It is used in papermaking as a wet-end additive for surface sizing. Ge-nerally, CMC do not attach on cellulosic fibers due to the electrostatic repulsion between the anionic polyelectrolyte and the negatively charged cellulosic sur-faces. [8] According the literature, CMC can be adsorbed by controlling the de-gree of substitution (DS) of the polymer. Where, CMC with high DS was adsorbed to the fibers surface. [8,9]

The industrial effluents are threate-ning the environment because of the to-xic heavy metals (e.g., copper, lead, cad-mium and mercury) that include. Heavy metals are causing various diseases and disorders due to their non-biodegradabi-lity and accumulation in plants, animals and human bodies. Consequently, nu-merous studies have been done to elimi-nate the risks of heavy metals in waste streams. Adsorption, filtration, ion ex-change, electrochemical treatment, che-mical precipitation and reverse osmosis were used for removing of heavy metals for such purpose. The adsorption me-

thod has been recognized as simple and low-cost methods for removing metal ions existing in waste streams. Some adsorbents such as clays, hydroxyapatite, silica gels, activated carbons, agricultural wastes, biomass, natural and synthetic polymers and zeolites were developed recently. [10-14] The interactions bet-ween the functional groups that are pre-sent on the surfaces of the coagulant or adsorbents with heavy metals facilitate the treatment of liquid wastes. [15]

Hydroxyapatite is a most important inorganic ingredient of the hard tissue (teeth and bone) in the human body due to it has good mechanical properties and their bioactivity [16]. Recently, it attrac-ted enormous attention because of its high capacity for deduction of divalent heavy metal ions from aqueous solu-tions [17, 18]. Many researchers have been carried out on HA to know their adsorption mechanism for heavy metals

Preparation and Characterization of CMC/HA-NPs/pulp Nanocom-posites for the removal of heavy Metal Ions

AuthorsM.E. Abd El-Aziz, Essam Saber, M.A. El-Khateeb, Dokki Giza, Egypt

Corresponding Author:M.E. AbdEl-AzizPolymers and pigments Depart-ment, National Research Centre,33 El Bohouthst.P.O. 12622, Dokki Giza, EgyptE-Mail: [email protected]


37KGK · 04 2019www.kgk-rubberpoint.de

from aqueous solutions and to estimate its usage for environmental treatment [17-19]. In general, the adsorption of heavy metal ions on HA is becoming a hopeful way for curing of wastewater and soil. However, the recovery of this material after removing heavy metal ions from wastewater is difficult due to the HA is usually provided in powder or pellets form [20].

The composite materials containing natural or synthetic polymers and inor-ganic materials, which used as the adsor-bents, have attracted great attention due to their combined advantages. Polyacryl-amide composites with hydroxyapatite [20] and bentonite [21] as adsorbents hydrogel were synthesis and their remo-val property of lead ions was investiga-ted. Also cellulose/hydroxyapatite nano-composites were prepared and their ad-sorption of fluoride from drinking water was investigated. [22]

This work aims to study the effect of addition of HA-NPs blended with the carboxymethyl cellulose on the mechani-cal and physical properties of the paper sheets (RWP and BWP). Also the adsorp-tion capacity of the produced nanocom-posites paper sheets for some selected ions was studied.

Materials and methods

MaterialsIn this study, two different pulps were used to prepare paper sheets according to Swedish standard method (SCA). The first one was recycled wastepaper pulp (RWP) and the second one was bleached wood pulp (BWP) which delivered from Quna (paper mill- Quna).

All the chemicals used for preparation were of analytical grade. Calcium chlori-de dihydrate, sodium orthophosphate dodehydrate, and carboxymethyl cellulo-se sodium salt (CMC) were obtained from Sigma-Aldrich chemical Company. Sodium hydroxide (NaOH) was purchased from S.D. Fine-Chem.

Methods

Preparation of HydroxyapatiteCalcium chloride dihydrate (CaCl2·2H2O) was dissolved in double-distilled water (dd-H2O) 5.8g/100ml to form solution (A). A solution of Na3PO4·12H2O (9.12g/100ml) was prepared and adjusted to pH 13 using 0.36 g of NaOH to form solution (B). Solu-tion (A) was then added into solution (B) drop by drop under constant vigorous stir-

ring at room temperature. The molar ratio of Ca/P was fixed at 1.67. The solution becomes turbid, and a white precipitate is observed. The white precipitate was col-lected using centrifuge at 5000 rpm and the supernatant was accordingly discard-ed. The white precipitate was then re-suspended into dd-H2O to rinse away the NaCl salt which obtained as a byproduct. The washing and centrifugation steps were repeated at least 3 times to ensure the complete removal of NaCl. The white precipitate obtained was then air dried in an oven at 70°C for 72 h and ground to a fine powder. [23]

Preparation of paper sheetBoth RWP and BWP were soaked in dd-H2O (1.5g/100ml) then 0.2 g of CMC was added. After that the pH of the solution was adjusted at 12.5 by NaOH, and then the solution heated at 60°C under stir-ring for 2 h. The pulp was washed with distilled water several times to remove the excess of NaOH. [8, 9]After that the HA-NPs were added with different ratio (0, 2.5, 5, 7.5 and 10 wt %) with respect to pulp.

Hand paper sheets with a grammage of over 68 g/m2 was made according to Swedish standard method (SCA). The hand paper sheets were conditioned at 25°C and 50% relative humidity for 24 h before testing. [24]

Characterization

Infrared (IR) spectral analysis FT-IR spectra of nanomaterial and paper cheat were recorded in the range of 400–4000 cm-1on Shimadzu8400S FT-IR Spec-trophotometer.

X-ray diffraction (XRD)The crystal structure of HA-NPs was ob-tained using Philips X-ray diffractometer (PW 1930 generator, PW 1820 goniome-ter) with CuK radiation source (45 kV, 40 mA, with λ= 0.15418 nm). The scans of the analysis were run in 2θ range of 5 to 70º with step size of 0.02 and step time of 1s.

Transmission Electron Microscope (TEM) The morphological and particles size of nanomaterial was demonstrated by us-ing TEM model JEM-1230, Japan, operat-ed at 120 kV, with maximum magnifica-tion of 600X103 and a resolution until 0.2 nm. A drop of an aqueous dispersion of the nanomaterial was placed on a carbon-coated copper grid and allowed to dry in air before characterization.

Scanning Electron Microscope (SEM)The surface morphology of paper sheet, and paper sheet nanocomposite were analyzed using SEM (JSM 6360LV, JEOL/Noran). The microscope was attached to a dispersive energy spectrometer (EDS). The images were obtained using an ac-celerating voltage of 10–15 kV. EDX anal-ysis was carried out to be supporting in-formation the presence of HA-NPs in the prepared nanocomposite.

Mechanical properties The tensile properties of the paper sheets are tested with a testing machine, as specified in the TAPPI standard T 494 om-01, The untreated and treated paper samples by different HA-NPs ratio were kept in the conditioned room for 24 h, and the testing of tensile strength in a standard atmosphere (at temperature of

Fig. 1: FT-IR spectrum of HA-NPs (a), CP/CMC paper scheet (b) and CP/CMC/HA-NPs paper sheet nanocomposite (c).

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23 ± 1°C and relative humidity (RH) 50 ± 0.2%.[25] Tensile testing was carried out on 15 mm wide strips between jaws set 100 mm apart, using a universal testing machine, model 4201 from Instorn Cor-poration equipped with a tension cell of 500N at a stretching speed of 5mm/min.

Water AbsorptionThe water absorption of the prepared paper sheets nanocomposites was evalu-ated by the procedure described by Abdel Moulehet [26]. Pieces of the prepared films were cut into small samples with dimensions of 6×6 cm 2×0.5 mm. The samples were weighed and then soaked in distilled water at 25°C for overnight. Next, the samples were removed, blotted to remove the excess water on the sur-face and then immediately weighed. The difference between the mass after a giv-en time of immersion and the initial mass is used to determine the water ab-sorption. The percentage weight gain (PWG) was calculated according to the following equation.

(1)

Where Wo is the weight of the sample before soaking in water and Wf is the

weight of the sample after soaking in water.

Removal of the metal ions Batch studies were performed using Copper (Cu), cadmium (Cd) and Iron (Fe) ions solutions with known concentra-tions (250 ppm) which prepared by dis-solving CuSO4, CdCl2 and FeSO4.7H2O in distilled water, respectively. 0.1 g of pa-per sheets nanocomposites were added to 20 mL of metal solutions and shaken for two hours. The final metal ions con-centrations were measured using atomic absorption spectrophotometer (Perkin-Elmer 3110, USA). The removal efficiency percent (R %) for sorbents toward metals ions are calculated by the following equations:

Where CO is the initial concentration of ions in solution and Ct is the concentra-tion of ions in solution after time (t).

Results and discussion

FT-IR studies The FT-IR spectra of hydroxyapatite nan-oparticles and paper sheet nanocompos-

ites are demonstrated in Fig. 1. The Fig. 1a shown the absorption bands at 3442, 1632 and 1457cm−1 due to the stretching and the bending vibrations of the O-H groups, respectively while the bands at 1039, 874, 603 and 568 cm-1 correspond to the (PO4)3+ group of HA-NPs. [27]

Furthermore, Fig. 1b shows absorp-tion band at 3433 cm-1 ascribed to OH stretching. While C-H stretching was rep-resented by band at 2929 cm-1, although the signals at 1400 and 1000 cm-1 were indicative of CH2. The peak at 1627 and 638 cm-1 conformable to the C=O stretch-ing of hemicelluloses and b-glycosidic linkage in cellulose, respectively [28]. While, Fig. 1c shown the corresponding spectra of paper sheet nanocomposites CP/CMC/HA-NPs, all major characteristic bands of HA-NPs and cellulose are pre-sented.

XRD analysisFig. 2 shows the XRD diffraction pattern of HA-NPs. The sharp peak at 2θ=25.9° represents a good crystallization and growth preference on the (002) crystal plane. Also it exposed plans at (002), (112), (300) and (202) corresponding to 2θ at 25.96°, 32.07°, 33.1°, and 34°, re-spectively. [27] The crystal size of HA-NPs was 5.9 nm.Calculations were carried out from the full width at half maximum (FWHM (β)) of the diffraction peaks using Debye-Scherer’s method [29] by applying this equation,

(2)

Where the X-ray wavelength (λ) equal 1.5403, (k) is Scherer’s constant equal 0.92, (β) is the full width at half maxi-mum (FWHM) intensity of a Bragg reflec-tion excluding instrumental broadening, (θ) is the Bragg’s angle and (d) is the aver-age crystalline dimension perpendicular to the reflecting phases.

Morphological examinationFig. 3 illustrates the TEM image of the HA-NPs. It can be demonstrated that the prepared HA-NPs have particles size less than 50nm. Furthermore, the surface morphology of the prepared paper sheets was shown in Fig. 4 and their cor-responding EDX.

The scanning electron microscopy (SEM) images of the paper sheets support the deposition of HA-NPs as apparent in Fig. 4. Simultaneously, the EDX confirmed the presence of HA-NPs in the prepared paper sheet as shown in Fig. 4 (b, c).

Fig. 2: XRD diffraction pattern of hydroxyapatite nanoparticles

Fig. 3: TEM image of HA-NPs at two different magnification

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1 Water absorption behavior of RWP/CMC with HA-NPs paper sheets

Sample no. HA-NPs Wt%/RWP Water absorption %

1 0.0 4582 2.5% 3893 5% 368

4 7.5% 3575 10% 289

Mechanical PropertiesThe tensile strength, young’s modulus and the maximum load of the paper sheets nanocomposites for RWP/CMC/HA-NPs and BWP/CMC/HA-NPs are pre-sented in Fig. 5. It was found that the tensile strength and the maximum load of the paper sheet nanocomposites in-creases with increasing HA-NPs up to 2.5 and 7.5% for both of RWP/CMC/HA-NPs and BWP/CMC/HA-NPs, respectively. Al-so the young’s modulus increases with increasing HA-NPs up to 2.5 and 5% for RWP/CMC/HA-NPs and BWP/CMC/HA-NPs, respectively.

Many researches were found that the mechanical properties of polymers can be enhanced by incorporating nanoparticles, which are mainly added to polymers for decreasing the cost as well as enhancing the stiffness. The mechanical properties were improved when the nanoparticles are dispersed homogeneously in the poly-mer matrix; otherwise the agglomerated nanoparticles would cause the drop in the mechanical properties of polymers mat-rix. [30- 32] In addition, from Fig. 5 (a,c) the tensile strength and the maximum load of the paper sheets nanocomposites for RWP/CMC/HA-NPs are lower than that of BWP/CMC/HA-NPs, this may be due to the ratio of virgin fiber in BWP are higher than that in RWP.[33]

Water AbsorptionThe paper sheets nanocomposites were soaking in water for overnight to study their water absorption behavior then the water absorption was calculated using equation 1. The water absorption capac-ity of RWP/CMC/HA-NPs higher than BWP/CMC/HA-NPs paper sheets nano-composites Tables (1, 2).This is due to the hydrophobicity of the recycled wastepa-per fibers which have a high tendency to water absorption, where the water ab-sorption in fibers composite is depend-ent on several factors such as orientation of fibers, fiber loading, surface protec-tion, permeability of fibers, void content, hydrophilicity of each components, and the area of exposed surfaces. In addition, the water absorption increased by in-creasing the fiber content attributed to increase the hydrophilic nature of the fibers. Furthermore, the presence of great number of porous tubular struc-tures in fiber facilitates the diffusion of water by the so-called capillary action. Same trend is observed for the compos-ites prepared by compression moulding. [34, 35]

Also, it was found that the water ab-sorption capacity of the paper sheets nanocomposites decreases by increasing

Fig. 4: SEM image of CP/CMC (a), RWP/CMC/HA-NPs (b), BWP/CMC/HA-NPs(c) and their corresponding EDEX.

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the HA-NPs loading for RWP/CMC/HA-NPs and BWP/CMC/HA-NPs, respectively, Tables (1 and 2). Similar behavior is no-



ted for the composites prepared from hydroxyapatite and cellulose acetate [36].

Cadmium, iron and copper removalFigs. 6 (a, b and c) show the performance of RWP/CMC/HA-NPs and BWP/CMC/HA-NPs paper sheets nanocomposites for removal of cadmium, iron and copper ions from water. It is clear that the re-moval shows the same trend in all met-

als. The removal of ions attributed to the presence of HA-NPs in the composite. The general mechanism for eliminated the divalent cations by HA-NPs has been studied by many researches. [17, 20] Where the metal ions (M+2) were ad-sorbed on the HA-NPs surfaces followed by the ion exchange reaction between M+2 and Ca2+ of HA-NPs. [20]

The mechanism of ion exchange reac-tion was expressed as:

Ca10(PO4)6 .(OH)2+ xM+2 → xCa2+ + Ca10-XMX(PO4)6 .(OH)2

ConclusionsAddition of hydroxyapatite nanoparti-cles greatly improved the mechanical properties and water absorption ability of the treated paper sheets. The en-hancement was extended to the removal of Cd, Fe and Cu ions.

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Fig. 5: The impact of various loadings of HA-NPs in RWP/CMC/HA-NPs and BWP/CMC/ HA-NPs paper sheets nanocomposites on (a) Tensile Strength (MPa), (b) Young`s modulus (MPa) and (c) Max. Load (N).

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2 Water absorption behavior of BWP/CMC with HA-NPs paper sheets

Sample no. HA-NPs Wt%/BWP Water absorption %

1 0.0 3452 2.5% 2853 5% 263

4 7.5% 2585 10% 254



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Fig. 6: The effect of various loadings of HA-NPs in RWP/CMC/HA-NPs and BWP/CMC/ HA-NPs paper sheets nanocomposites on adsorption of a) cadmium ions, b) iron ions and c) copper ions.

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