Synthesis and characterization of organic montmorillonite-polyvinyl alcohol-co-polyacrylic nanocomposite hydrogel for heavy metal uptake in water

Mona Mohsen; Ehsan Gomaa; Nabila Ahmed Mazaid; Reem Mohammed; Mona Mohsen; Ehsan Gomaa; Nabila Ahmed Mazaid; Reem Mohammed

doi:10.3934/matersci.2017.5.1122

AIMS Materials Science

2017, Volume 4, Issue 5: 1122-1139. doi: 10.3934/matersci.2017.5.1122

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Research article

Synthesis and characterization of organic montmorillonite-polyvinyl alcohol-co-polyacrylic nanocomposite hydrogel for heavy metal uptake in water

1.
Physics Department, Faculty of Science, Ain Shams University, Abbassia, 11566, Cairo, Egypt
2.
Polymer Chemistry Department—National Center for Radiation Research and Technology, Atomic Energy Authority, Egypt

Received: 26 July 2017 Accepted: 26 October 2017 Published: 01 November 2017

In the present work, preparation of organic montmorillonite-polyvinyl alcohol-co-polyacrylic (OMMT-PVA/AAc) nanocomposite hydrogels are performed with different OMMT ratios ranging from 1.3 to 15% using γ irradiation as initiator to induce crosslink network structure. These nanocomposites hydrogels are prepared to use in heavy metals water decontamination. The effect of clay ratio and absorbed dose on gel fraction and swelling% has been investigated. It is found that the gel fraction increases up to 92% with increasing the loaded OMMT to 15%, whereas the swelling% reaches its maximum value at a ratio of nanoscale clay of 6% and at an absorbed dose of 4 kGy. The thermal stability of PVA/AAc hydrogel and OMMT-PVA/AAc nanocomposite hydrogels has been determined by thermogravimetric analysis (TGA), which indicated a higher thermal stability of the nanocomposite hydrogel. The FTIR spectral analysis has identified the bond structure of the PVA/AAc hydrogel and the OMMT-PVA/AAc nanocomposite. The nanostructure of the composite as well as the degree of exfoliation of clay are studied by X-ray diffraction (XRD). Its free volume holes parameters (size and fraction) are investigated by means of positron annihilation lifetime spectroscopy (PALS).
After loading the bulk and nanocomposites hydrogels with different heavy metals (Cu²⁺, Co²⁺ and Ni²⁺), UV spectroscopy is applied to determine the metal ion concentration before and after treatment. The distribution of heavy metals on the hydrogels is determined by energy dispersive X-ray (EDX). The factors affecting the heavy metal uptake, such as contact time, pH and metal ion concentration of solutions are studied.
The results have shown that, the presence of OMMT increases the thermal stability of PVA/AAc due to the hydrogen bond formed between them which, is confirmed by FTIR. In addition, the resulting gel fraction after irradiation with relatively low gamma absorbed dose increased by 120%, enabling the sample to be reused for several times. In addition, the metal adsorption has increased from 194, 185, 144 mg/g for Cu²⁺, Co²⁺ and Ni²⁺ respectively in case of previously prepared PVA/AAc hydrogel to 835, 785, 636 mg/g for Cu²⁺, Co²⁺ and Ni²⁺ respectively for OMMT-PVA/AAc nanocomposite.

Keywords:

Citation: Mona Mohsen, Ehsan Gomaa, Nabila Ahmed Mazaid, Reem Mohammed. Synthesis and characterization of organic montmorillonite-polyvinyl alcohol-co-polyacrylic nanocomposite hydrogel for heavy metal uptake in water[J]. AIMS Materials Science, 2017, 4(5): 1122-1139. doi: 10.3934/matersci.2017.5.1122

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Abstract

1. Introduction

We consider the following family of nonlinear oscillators

$\begin{equation} y_{zz}+k(y)y_{z}^{3}+h(y)y_{z}^{2}+f(y)y_{z}+g(y) = 0, \end{equation}$

(1.1)

where $k$ , $h$ , $f\neq0$ and $g\neq0$ are arbitrary sufficiently smooth functions. Particular members of (1.1) are used for the description of various processes in physics, mechanics and so on and they also appear as invariant reductions of nonlinear partial differential equations ^[1,2,3].

Integrability of (1.1) was studied in a number of works ^{[4,5,6,7,8,9,10,11,12,13,14,15,16]}. In particular, in ^[15] linearization of (1.1) via the following generalized nonlocal transformations

$\begin{equation} w = F(y), \quad d\zeta = (G_{1}(y)y_{z}+G_{2}(y))dz. \end{equation}$

(1.2)

was considered. However, equivalence problems with respect to transformations (1.2) for (1.1) and its integrable nonlinear subcases have not been studied previously. Therefore, in this work we deal with the equivalence problem for (1.1) and its integrable subcase from the Painlevé-Gambier classification. Namely, we construct an equivalence criterion for (1.1) and a non-canonical form of Ince Ⅶ equation ^[17,18]. As a result, we obtain two new integrable subfamilies of (1.1). What is more, we demonstrate that for any equation from (1.1) that satisfy one of these equivalence criteria one can construct an autonomous first integral in the parametric form. Notice that we use Ince Ⅶ equation because it is one of the simplest integrable members of (1.1) with known general solution and known classification of invariant curves.

Moreover, we show that transformations (1.2) preserve autonomous invariant curves for equations from (1.1). Since the considered non-canonical form of Ince Ⅶ equation admits two irreducible polynomial invariant curves, we obtain that any equation from (1.1), which is equivalent to it, also admits two invariant curves. These invariant curves can be used for constructing an integrating factor for equations from (1.1) that are equivalent to Ince Ⅶ equation. If this integrating factor is Darboux one, then the corresponding equation is Liouvillian integrable ^[19]. This demonstrates the connection between nonlocal equivalence approach and Darboux integrability theory and its generalizations, which has been recently discussed for a less general class of nonlocal transformations in ^[20,21,22].

The rest of this work is organized as follows. In the next Section we present an equivalence criterion for (1.1) and a non-canonical form of the Ince Ⅶ equation. In addition, we show how to construct an autonomous first integral for an equation from (1.1) satisfying this equivalence criterion. We also demonstrate that transformations (1.2) preserve autonomous invariant curves for (1.1). In Section 3 we provide two examples of integrable equations from (1.1) and construct their parametric first integrals, invariant curves and integrating factors. In the last Section we briefly discuss and summarize our results.

2. Main results

We begin with the equivalence criterion between (1.1) and a non-canonical form of the Ince Ⅶ equation, that is ^[17,18]

$\begin{equation} w_{\zeta\zeta}+3w_{\zeta}+\epsilon w^{3}+2w = 0. \end{equation}$

(2.1)

Here $\epsilon\neq0$ is an arbitrary parameter, which can be set, without loss of generality, to be equal to $\pm 1$ .

The general solution of (1.1) is

$\begin{equation} w = {\rm e}^{-(\zeta-\zeta_{0})}\rm{cn}\left\{\sqrt{\epsilon}({\rm e}^{-(\zeta-\zeta_{0})}-C_{1}),\frac{1}{\sqrt{2}}\right\}. \end{equation}$

(2.2)

Here $\zeta_{0}$ and $C_{1}$ are arbitrary constants and $\rm{cn}$ is the Jacobian elliptic cosine. Expression (2.2) will be used below for constructing autonomous parametric first integrals for members of (1.1).

The equivalence criterion between (1.1) and (2.1) can be formulated as follows:

Theorem 2.1. Equation (1.1) is equivalent to (2.1) if and only if either

$\begin{equation} \begin{gathered} (I)\quad 25515lgp^{2}q_{y}+2352980l^{10}+\left(3430q-6667920p^{3}\right) l^{5}\\ -14580qp^{3}-10q^{2}-76545lgqpp_{y} = 0, \end{gathered} \end{equation}$

(2.3)

$\begin{equation} \begin{gathered} (II)\quad 343l^{5}-972p^{3} = 0, \end{gathered} \end{equation}$

(2.4)

holds. Here

$\begin{equation} \begin{gathered} l = 9(fg_{y}-gf_{y}+fgh-3kg^{2})-2f^{3}, \quad p = gl_{y}-3lg_{y}+l(f^{2}-3gh),\\ q = 25515g_{y}lp^{2}-5103lgpp_{y}+686l^{5}-8505p^{2}\left( f^{2}-3gh \right) l+6561p^{3}. \end{gathered} \end{equation}$

(2.5)

The expression for $G_{2}$ in each case is either

$\begin{equation} (I) \quad G_{2} = \frac {126 l^{2}qp^{2}}{470596 l^{10}- \left( 1333584 p^{3}+1372 q \right) l^{5}+q^{2}}, \end{equation}$

(2.6)

$\begin{equation} (II) \quad G_{2}^{2} = -\frac{49l^{3}G_{2}+9p^{2}}{189pl}. \end{equation}$

(2.7)

In all cases the functions $F$ and $G_{1}$ are given by

$\begin{equation} F^{2} = \frac{l}{81\epsilon G_{2}^{3}}, \quad G_{1} = \frac{G_{2}(f-3G_{2})}{3g}. \end{equation}$

(2.8)

Proof. We begin with the necessary conditions. Substituting (1.2) into (2.1) we get

$\begin{equation} y_{zz}+k(y)y_{z}^{3}+h(y)y_{z}^{2}+f(y)y_{z}+g(y) = 0, \end{equation}$

(2.9)

where

$\begin{equation} \begin{gathered} k = \frac{FG_{1}^{3}(\epsilon F^{2}+2)+3G_{1}^{2}F_{y}+G_{1}F_{yy}-F_{y}G_{1,y}}{G_{2}F_{y}}, \\ h = \frac{G_{2}F_{yy}+(6G_{1}G_{2}-G_{2,y})F_{y}+3FG_{2}G_{1}^{2}(\epsilon F^{2}+2)}{G_{2}F_{y}},\\ f = \frac{3G_{2}(F_{y}+FG_{1}(\epsilon F^{2}+2))}{F_{y}}, \quad g = \frac{FG_{2}^{2}(\epsilon F^{2}+2)}{F_{y}}. \end{gathered} \end{equation}$

(2.10)

As a consequence, we obtain that (1.1) can be transformed into (2.1) if it is of the form (2.9) (or (1.1)).

Conversely, if the functions $F$ , $G_{1}$ and $G_{2}$ satisfy (2.10) for some values of $k$ , $h$ , $f$ and $g$ , then (1.1) can be mapped into (2.1) via (1.2). Thus, we see that the compatibility conditions for (2.10) as an overdertmined system of equations for $F$ , $G_{1}$ and $G_{2}$ result in the necessary and sufficient conditions for (1.1) to be equivalent to (2.1) via (1.2).

To obtain the compatibility conditions, we simplify system (2.10) as follows. Using the last two equations from (2.10) we find the expression for $G_{1}$ given in (2.8). Then, with the help of this relation, from (2.10) we find that

$\begin{equation} 81\epsilon F^{2}G_{2}^{3}-l = 0, \end{equation}$

(2.11)

and

$\begin{equation} \begin{gathered} 567lG_{2}^{3}+(243lgh-81lf^{2}-81gl_{y}+243lg_{y})G_{2}-7l^{2} = 0,\\ 243lgG_{2,y}+324lG_{2}^{3}-81gl_{y}G_{2}+2l^{2} = 0, \end{gathered} \end{equation}$

(2.12)

Here $l$ is given by (2.5).

As a result, we need to find compatibility conditions only for (2.12). In order to find the generic case of this compatibility conditions, we differentiate the first equation twice and find the expression for $G_{2}^{2}$ and condition (2.3). Differentiating the first equation from (2.12) for the third time, we obtain (2.6). Further differentiation does not lead to any new compatibility conditions. Particular case (2.4) can be treated in the similar way.

Finally, we remark that the cases of $l = 0$ , $p = 0$ and $q = 0$ result in the degeneration of transformations (1.2). This completes the proof.

As an immediate corollary of Theorem 2.1 we get

Corollary 2.1. If coefficients of an equation from (1.1) satisfy either (2.3) or (2.4), then an autonomous first integral of this equation can be presented in the parametric form as follows:

$\begin{equation} y = F^{-1}(w), \quad y_{z} = \frac{G_{2}w_{\zeta}}{F_{y}-G_{1}w_{\zeta}}\,. \end{equation}$

(2.13)

Here $w$ is the general solution of (2.1) given by (2.2). Notice also that, formally, (2.13) contains two arbitrary constants, namely $\zeta_{0}$ and $C_{1}$ . However, without loss of generality, one of them can be set equal to zero.

Now we demonstrate that transformations (1.2) preserve autonomous invariant curves for equations from (1.1).

First, we need to introduce the definition of an invariant curve for (1.1). We recall that Eq (1.1) can be transformed into an equivalent dynamical system

$\begin{equation} y_{z} = P, \quad u_{z} = Q, \quad P = u, \quad Q = -k u^{3}-h u^{2}-f u -g. \end{equation}$

(2.14)

A smooth function $H(y, u)$ is called an invariant curve of (2.14) (or, equivalently, of (1.1)), if it is a nontrivial solution of ^[19]

$\begin{equation} PH_{y}+QH_{u} = \lambda H, \end{equation}$

(2.15)

for some value of the function $\lambda$ , which is called the cofactor of $H$ .

Second, we need to introduce the equation that is equivalent to (1.1) via (1.2). Substituting (1.2) into (1.1) we get

$\begin{equation} w_{\zeta\zeta}+\tilde{k}w_{\zeta}^{3}+\tilde{h}w_{\zeta}^{2}+\tilde{f}w_{\zeta}+\tilde{g} = 0, \end{equation}$

(2.16)

where

$\begin{equation} \begin{gathered} \tilde{k} = \frac{kG_{2}^{3}-gG_{1}^{3}+(G_{1,y}-hG_{1})G_{2}^{2}+(fG_{1}-G_{2,y})G_{1}G_{2}}{F_{y}^{2}G_{2}^{2}},\\ \tilde{h} = \frac{(hF_{y}-F_{yy})G_{2}^{2}-(2fG_{1}-G_{2,y})G_{2}F_{y}+3gG_{1}^{2}F_{y}}{F_{y}^{2}G_{2}^{2}},\\ \tilde{f} = \frac{fG_{2}-3gG_{1}}{G_{2}^{2}}, \quad \tilde{g} = \frac{gF_{y}}{G_{2}^{2}}. \end{gathered} \end{equation}$

(2.17)

An invariant curve for (2.16) can be defined in the same way as that for (1.1). Notice that, further, we will denote $w_{\zeta}$ as $v$ .

Theorem 2.2. Suppose that either (1.1) possess an invariant curve $H(y, u)$ with the cofactor $\lambda(y, u)$ or (2.16) possess an invariant curve $\widetilde{H}(w, v)$ with the cofactor $\tilde{\lambda}(w, v)$ . Then, the other equation also has an invariant curve and the corresponding invariant curves and cofactors are connected via

$\begin{equation} \begin{gathered} H(y,u) = \widetilde{H}\left(F,\frac{F_{y}u}{G_{1}u+G_{2}}\right), \quad \lambda(y,u) = (G_{1}u+G_{2})\tilde{\lambda}\left(F,\frac{F_{y}u}{G_{1}u+G_{2}}\right). \end{gathered} \end{equation}$

(2.18)

Proof. Suppose that $\widetilde{H}(w, v)$ is an invariant curve for (2.16) with the cofactor $\widetilde{\lambda}(w, v)$ . Then it satisfies

$\begin{equation} v\widetilde{H}_{w}+(-\tilde{k} v^{3}-\tilde{h} v^{2}-\tilde{f} v -\tilde{g})\widetilde{H}_{v} = \widetilde{\lambda}\widetilde{H}. \end{equation}$

(2.19)

Substituting (1.2) into (2.19) we get

$\begin{equation} uH_{y}+(-k u^{3}-h u^{2}-f u-g)H = (G_{1}u+G_{2}) \tilde{\lambda}\left(F,\frac{F_{y}u}{G_{1}u+G_{2}}\right) H . \end{equation}$

(2.20)

This completes the proof.

As an immediate consequence of Theorem 2.2 we have that transformations (1.2) preserve autonomous first integrals admitted by members of (1.1), since they are invariant curves with zero cofactors.

Another corollary of Theorem 2.2 is that any equation from (1.1) that is connected to (2.1) admits two invariant curves that correspond to irreducible polynomial invariant curves of (2.1). This invariant curves of (2.1) and the corresponding cofactors are the following (see, ^[23] formulas (3.18) and (3.19) taking into account scaling transformations)

$\begin{equation} \widetilde{H} = \pm i \sqrt{-2\epsilon}(v+w)+w^{2}, \quad \tilde{\lambda} = \pm \sqrt{-2\epsilon}w-2. \end{equation}$

(2.21)

Therefore, we have that the following statement holds:

Corollary 2.2. If coefficients of an equation from (1.1) satisfy either (2.3) or (2.4), then is admits the following invariant curves with the corresponding cofactors

$\begin{equation} H = \pm i \sqrt{-2\epsilon}\left(\frac{F_{y}u}{G_{1}u+G_{2}}+F\right)+F^{2}, \quad \lambda = \left(G_{1}u+G_{2}\right)\left(\pm \sqrt{-2\epsilon}F-2\right). \end{equation}$

(2.22)

Let us remark that connections between (2.1) and non-autonomous variants of (1.1) can be considered via a non-autonomous generalization of transformations (1.2). However, one of two nonlocally related equations should be autonomous since otherwise nonlocal transformations do not map a differential equation into a differential equation ^[5].

In this Section we have obtained the equivalence criterion between (1.1) and (2.1), that defines two new completely integrable subfamilies of (1.1). We have also demonstrated that members of these subfamilies posses an autonomous parametric first integral and two autonomous invariant curves.

3. Examples

In this Section we provide two examples of integrable equations from (1.1) satisfying integrability conditions from Theorem 2.1.

Example 1. One can show that the coefficients of the following cubic oscillator

$\begin{equation} y_{zz}-\frac{12\epsilon \mu y}{(\epsilon \mu^{2}y^{4}+2)^{2}}y_{z}^{3}-6\mu y y_{z}+2\mu^{2}y^{3}(\epsilon\mu^{2}y^{4}+2) = 0, \end{equation}$

(3.1)

satisfy condition (2.3) from Theorem 2.1. Consequently, Eq (3.1) is completely integrable and its general solution can be obtained from (2.2) by inverting transformations (1.2). However, it is more convenient to use Corollary 2.1 and present the autonomous first integral of (3.1) in the parametric form as follows:

$\begin{equation} y = \pm\sqrt{\frac{w}{\mu}}, \quad y_{z} = \frac{w(\epsilon w^{2}+2) w_{\zeta}}{2w_{\zeta}+w(\epsilon w^{2}+2)}, \end{equation}$

(3.2)

where $w$ is given by (2.2), $\zeta$ is considered as a parameter and $\zeta_{0}$ , without loss of generality, can be set equal to zero. As a result, we see that (3.1) is integrable since it has an autonomous first integral.

Moreover, using Corollary 2.2 one can find invariant curves admitted by (3.1)

$\begin{equation} \begin{gathered} H_{1,2} = \frac{y^{4}\left[(\sqrt{2}\pm \sqrt{-\epsilon}\mu y^{2})^{2}(\sqrt{2}\mp\sqrt{-\epsilon}\mu y^{2})+2(\epsilon\mu y^{2}\mp\sqrt{-2\epsilon})u\right]}{2\mu^{2}y^{2}(\epsilon\mu^{2}y^{4}+2)-4u},\\ \lambda_{1,2} = \pm\frac{2(\mu y^{2}(\epsilon\mu^{2}y^{4}+2)-2u)(\sqrt{-2\epsilon}\mu y^{2}\mp 2)}{y(\epsilon\mu^{2}y^{4}+2)} \end{gathered} \end{equation}$

(3.3)

With the help of the standard technique of the Darboux integrability theory ^[19], it is easy to find the corresponding Darboux integrating factor of (3.1)

$\begin{equation} M = \frac{(\epsilon \mu^{2}y^{4}+2)^{\frac{9}{4}}}{(2\epsilon u^{2}+(\epsilon\mu^{2}y^{4}+2)^{2})^{\frac{3}{4}}(\mu y^{2}(\epsilon \mu^{2}y^{4}+2)-2u)^{\frac{3}{2}}}. \end{equation}$

(3.4)

Consequently, equation is (3.1) Liouvillian integrable.

Example 2. Consider the Liénard (1, 9) equation

$\begin{equation} y_{zz}+(b_{i}y^{i}){y_{z}}+a_{j}y^{j} = 0, \quad i = 0,\ldots 4, \quad j = 0,\ldots,9. \end{equation}$

(3.5)

Here summation over repeated indices is assumed. One can show that this equation is equivalent to (2.1) if it is of the form

$\begin{equation} y_{zz}-9(y+\mu)(y+3\mu)^{3}y_{z}+2y(2y+3\mu)(y+3\mu)^{7} = 0, \end{equation}$

(3.6)

where $\mu$ is an arbitrary constant.

With the help of Corollary 2.1 one can present the first integral of (3.6) in the parametric form as follows:

$\begin{equation} y = \frac{3\sqrt{-2\epsilon}\mu w}{2-\sqrt{-2\epsilon}w}, \quad y_{z} = \frac{7776 \sqrt{2} \epsilon \mu^{5} w w_{\zeta}}{(\sqrt{-2\epsilon}w-2)^{5}(2\sqrt{-\epsilon}w_{\zeta}+(\sqrt{2}\epsilon w +2\sqrt{-\epsilon})w)}, \end{equation}$

(3.7)

where $w$ is given by (2.2). Thus, one can see that (3.5) is completely integrable due to the existence of this parametric autonomous first integral.

Using Corollary 2.2 we find two invariant curves of (3.6):

$\begin{equation} H_{1} = \frac{y^{2}[(2y+3\mu)(y+3\mu)^{4}-2u)]}{(y+3\mu)^{2}[(y+3\mu)^{4}y-u]}, \quad \lambda_{1} = \frac{6\mu(u-y(y+3\mu)^{4})}{y(y+3\mu)}, \end{equation}$

(3.8)

and

$\begin{equation} H_{2} = \frac{y^{2}(y+3\mu)^{2}}{y(y+3\mu)^{4}-u}, \quad \lambda_{2} = \frac{2(2y+3\mu)(u-2y(y+3\mu)^{4})}{y(y+3\mu)}. \end{equation}$

(3.9)

The corresponding Darboux integrating factor is

$\begin{equation} M = \left[y(y+3\mu)^{4}-u\right]^{-\frac{3}{2}}\left[(2y+3\mu)(y+3\mu)^{4}-2u\right]^{-\frac{3}{4}}. \end{equation}$

(3.10)

As a consequence, we see that Eq (3.6) is Liouvillian integrable.

Therefore, we see that equations considered in Examples 1 and 2 are completely integrable from two points of view. First, they possess autonomous parametric first integrals. Second, they have Darboux integrating factors.

4. Conclusions and discussion

In this work we have considered the equivalence problem between family of Eqs (1.1) and its integrable member (2.1), with equivalence transformations given by generalized nonlocal transformations (1.2). We construct the corresponding equivalence criterion in the explicit form, which leads to two new integrable subfamilies of (1.1). We have demonstrated that one can explicitly construct a parametric autonomous first integral for each equation that is equivalent to (2.1) via (1.2). We have also shown that transformations (1.2) preserve autonomous invariant curves for (1.1). As a consequence, we have obtained that equations from the obtained integrable subfamilies posses two autonomous invariant curves, which corresponds to the irreducible polynomial invariant curves of (2.1). This fact demonstrate a connection between nonlocal equivalence approach and Darboux and Liouvillian integrability approach. We have illustrate our results by two examples of integrable equations from (1.1).

Acknowledgments

The author was partially supported by Russian Science Foundation grant 19-71-10003.

Conflict of interest

The author declares no conflict of interest in this paper.

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