Research article Topical Sections

Effect of hygrothermal conditioning on the mechanical and thermal properties of epoxy grouts for offshore pipeline rehabilitation

  • Offshore oil and gas pipelines are susceptible to corrosion and need rehabilitation to keep them operating in-service conditions. Fibre composite filled with epoxy-based grout is emerging as an effective repair and rehabilitation system for offshore pipelines performing underwater. In such applications, the infill grout is often subjected to moisture and elevated temperature along with compressive, tensile and localised stresses at the defect. Current standards and practices for composite repairs suggest detailed investigation of the fibre reinforced sleeve, while the characterisation of the infill material is yet to be conducted for performance evaluation. The present work investigates the mechanical and thermal properties of three epoxy grouts as candidates for infill in a grouted sleeve repair for underwater pipeline. An understanding on the effect of hygrothermal ageing on the grout properties for defining the period of 1000 hours as “long-term” according to ISO/TS 24817, in comparison to their unconditioned state, is also presented. The compressive and tensile strength of the unconditioned grouts ranges from 100–120 MPa, and 19–32 MPa, respectively, which indicates that these grouts are suitable for structural rehabilitation of the pipelines. Moreover, the glass transition temperatures, Tg and Tt of the unconditioned grouts are found to be within the ranges of 50–60 °C, and 80–90 °C, respectively, which are reduced by about 20°C after conditioning.

    Citation: Md Shamsuddoha, Md Mainul Islam, Thiru Aravinthan, Allan Manalo, Luke P. Djukic. Effect of hygrothermal conditioning on the mechanical and thermal properties of epoxy grouts for offshore pipeline rehabilitation[J]. AIMS Materials Science, 2016, 3(3): 832-850. doi: 10.3934/matersci.2016.3.832

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  • Offshore oil and gas pipelines are susceptible to corrosion and need rehabilitation to keep them operating in-service conditions. Fibre composite filled with epoxy-based grout is emerging as an effective repair and rehabilitation system for offshore pipelines performing underwater. In such applications, the infill grout is often subjected to moisture and elevated temperature along with compressive, tensile and localised stresses at the defect. Current standards and practices for composite repairs suggest detailed investigation of the fibre reinforced sleeve, while the characterisation of the infill material is yet to be conducted for performance evaluation. The present work investigates the mechanical and thermal properties of three epoxy grouts as candidates for infill in a grouted sleeve repair for underwater pipeline. An understanding on the effect of hygrothermal ageing on the grout properties for defining the period of 1000 hours as “long-term” according to ISO/TS 24817, in comparison to their unconditioned state, is also presented. The compressive and tensile strength of the unconditioned grouts ranges from 100–120 MPa, and 19–32 MPa, respectively, which indicates that these grouts are suitable for structural rehabilitation of the pipelines. Moreover, the glass transition temperatures, Tg and Tt of the unconditioned grouts are found to be within the ranges of 50–60 °C, and 80–90 °C, respectively, which are reduced by about 20°C after conditioning.


    A topological descriptor is a single number that represents a chemical structure in graph-theoretical terms via the molecular graph, they play a significant role in mathematical chemistry, especially in the QSPR/QSAR investigations. A topological descriptor is called a topological index if it correlates with a molecular property.

    Topological indices are used to understand physico-chemical properties of chemical compounds, since they capture the essence of some properties of a molecule in a single number. Several of the well-known topological indices based its computing as a sum of terms which correspond to edges where each term is obtained by a symmetric expression of the degree of both end points, e.g., harmonic, Randić connectivity, first and second Zagreb, atom-bound connectivity and Platt indices. Lately, researchers in chemistry and pharmacology have focused in topological indices based on degrees of vertices obtaining good results and showing that a number of these indices has turned out to be a useful tool, see [1] and references therein. Probably, Randić connectivity index (R) [2] is the most known. In fact, there exist hundreds of works about this molecular descriptor (see, e.g., [3,4,5,6,7,8] and the references therein). Trying to improve the predictive power of this index during many years, scientists proposed a great number of new topological descriptors based on degrees of vertices, similar to the Randić index. There are a lot of works showing the interest on these indices, see e.g., [9,10,11,12,13,14,15,16,17].

    The study of the exponential vertex-degree-based topological indices was initiated in [18] and has been successfully studied in [19,20,21,22,23,24,25]. The study of topological indices associated to exponential representations has been successfully studied in [12,14,20,22,26,27]. Cruz et al. mentioned in 2020 some open problems on the exponential vertex-degree-based topological indices of trees [28] and Das et al. show in 2021 the solution of two of those problems in [23]. In this sense, we work with generic exponential topological indices described below that allows us to improve some of the bounds given in [23] as well as obtain some new results.

    Along this work, given a graph G=(V(G),E(G)) and a symmetric function f:[1,)×[1,)R, we consider the general topological indices

    F(G)=uvE(G)f(du,dv),eF(G)=uvE(G)ef(du,dv).

    As usual, uv denotes an edge of the graph G connecting the vertices u and v, and dx denotes the degree of the vertex x. The family of the topological indices like the one to the right above are called exponential for obvious reasons.

    Two examples of those topological indices that have been extended to its exponential indices are the generalized atom-bound connectivity index, ABCα, and the generalized second Zagreb index, Mα2, defined respectively as

    ABCα(G)=uvE(G)(du+dv2dudv)α,
    Mα2(G)=uvE(G)(dudv)α.

    Then, their corresponding exponential indices are

    eABCα(G)=uvE(G)e(du+dv2dudv)α,
    eMα2(G)=uvE(G)e(dudv)α.

    The study of topological indices is often formalized mathematically as optimization problems on graphs. In general, those problems have been proven to be useful and quite difficult. Indeed, to obtain quasi-minimizing or quasi-maximizing graphs is a good strategy that is commonly used. Therefore, frequently, it is needed to find bounds on them which involve several parameters.

    Topological indices have been successfully applied to different branches of knowledge, such as chemistry, physics, biology, social sciences, etc. see [29,30,31,32,33]. In this direction, two of the most important theoretical and practical problems facing the study of topological indices are the following: the study of the extremal problems associated with topological indices and obtaining new inequalities relating different indices. This research has as fundamental contribution to face the above mentioned problems associated with the study of exponential vertex-degree-based topological indices. In particular, we solve some extremal problems related with the exponential vertex-degree-based topological indices eMα2 and eABCα. Also, we obtain new lower and upper optimal bounds for these general exponential indices.

    Throughout this work, G=(V(G),E(G)) denotes a (non-oriented) finite simple graph without isolated vertices. Given a graph G and vV(G), we denote by N(v) the set of neighbors of v, i.e., N(v)={uV(G)|uvE(G)}. We denote by Δ,δ,n,m the maximum degree, the minimum degree and the cardinality of the set of vertices and edges of G, respectively; thus, 1δΔ<n.

    We study in this section some optimization problems on the exponential index eMα2.

    Recall that we denote by N(w) the set of neighbors of w.

    Proposition 2.1. Let G be a graph with nonadjacent vertices u and v. If f is a symmetric function which is increasing in each variable, then eF(G+uv)>eF(G).

    Proof. Since f is increasing in each variable, we have ef(du+1,dw)ef(du,dw), ef(dv+1,dw)ef(dv,dw) and

    eF(G+uv)eF(G)=wN(u)(ef(du+1,dw)ef(du,dw))+wN(v)(ef(dv+1,dw)ef(dv,dw))+ef(du+1,dv+1)ef(du+1,dv+1)>0.

    Hence,

    eF(G+uv)>eF(G).

    For example, if we take α>0, f(x,y)=(xy)α, the cycle Cn with n>2 and remove one edge we obtain the path Pn, and we have eMa2(Cn)=ne4α, eMa2(Pn)=(n3)e4α+2e2α and eMa2(Cn)eMa2(Pn)=3e4α2e2α>0. Now if we take the complete graph Kn with n>2 and H is the graph obtained by removing an edge from Kn, we have eMa2(Kn)=n(n1)2e(n1)2α, eMa2(H)=((n2)(n3)2)e(n1)2α+2(n2)e[(n1)(n2)]α and eMa2(Kn)eMa2(H)=(2n3)e(n1)2α2(n2)e[(n1)(n2)]α>0. Thus, we have e(n1)α(n2)α>1>2n42n3.

    Given an integer n2, let G(n) be the set of graphs with n vertices.

    Given integers 1δ<n, let H(n,δ) be the set of graphs with n vertices and minimum degree δ

    We consider the optimization problem for the exponential index eMα2 on G(n).

    Theorem 2.2. Consider α>0 and an integer n2.

    (1) The unique graph that maximizes the eMα2 index on G(n) is the complete graph Kn.

    (2) If n is even, then the unique graph that minimizes the eMα2 index on G(n) is the disjoint union of n/2 paths P2. If n is odd, then the unique graph that minimizes the eMα2 index on G(n) is the disjoint union of (n3)/2 paths P2 and a path P3.

    Proof. Since α>0 we have that f(x,y)=(xy)α is an increasing function in each variable and so, we can apply Proposition 2.1. The first item is a direct consequence of Proposition 2.1.

    Assume first that n is even. Handshaking lemma gives 2mnδn. We have for any graph GG(n)

    eMα2(G)=uvE(G)e(dudv)αuvE(G)e=me12ne,

    and the equality in the bound is attained if and only if du=1 for every uV(G), i.e., G is the disjoint union of n/2 path graphs P2.

    Assume now that n is odd, and consider a graph GG(n). If du=1 for every uV(G), then handshaking lemma gives 2m=n, a contradiction since n is odd. Thus, there exists a vertex w with dw2. Handshaking lemma gives 2m(n1)δ+2n+1. We have

    eMα2(G)=uN(w)e(dudw)α+uvE(G),u,vwe(dudv)αuN(w)e2α+uvE(G),u,vwe2e2α+(m2)e2e2α+(n+122)e=2e2α+n32e,

    and the equality in the bound is attained if and only if du=1 for every uV(G){w}, and dw=2, i.e., G is the disjoint union of (n3)/2 path graphs P2 and a path graph P3.

    Note that for α=1, the result in Theorem 2.2 was obtained in [20,Theorem 2.2].

    If 1δ<Δ are integers, we say that a graph G is (Δ,δ)-pseudo-regular if there exists vV(G) with dv=Δ and du=δ for every uV(G){v}.

    In [34] appears the following result.

    Lemma 2.3. Consider integers 2k<n.

    (1) If kn is even, then there is a connected k-regular graph with n vertices.

    (2) If kn is odd, then there is a connected (k+1,k)-pseudo-regular graph with n vertices.

    Given integers 1δ<n, denote by Kδn the n-vertex graph with maximum degree n1 and minimum degree δ, obtained from the complete graph Kn1 and an additional vertex v in the following way: Fix δ vertices u1,,uδV(Kn1) and let V(Kδn)=V(Kn1){v} and E(Kδn)=E(Kn1){u1v,,uδv}.

    Figure 1 illustrates this construction by showing the graphs K26 and K36.

    Figure 1.  The graphs (a) K26, (b) K36.

    We consider now the optimization problem for the exponential index eMα2 on H(n,δ).

    Theorem 2.4. Consider α>0 and integers 1δ<n.

    (1) Then the unique graph in H(n,δ) that maximizes the eMα2 index is Kδn.

    (2) If δ2 and δn is even, then the unique graphs in H(n,δ) that minimize the eMα2 index are the δ-regular graphs.

    (3) If δ2 and δn is odd, then the unique graphs in H(n,δ) that minimize the eMα2 index are the (δ+1,δ)-pseudo-regular graphs.

    Proof. Given a graph GH(n,δ){Kδn}, fix any vertex uV(G) with du=δ. Since

    GG{vw:v,wV(G){u} and vwE(G)}=Kδn,

    Proposition 2.1 gives eMα2(Kδn)>eMα2(G). This proves item (1).

    Handshaking lemma gives 2mnδ.

    Since duδ for every uV(G), we obtain

    eMα2(G)=uvE(G)e(dudv)αuvE(G)eδ2α=meδ2α12nδeδ2α,

    and the equality in the bound is attained if and only if du=δ for every uV(G).

    If δn is even, then Lemma 2.3 gives that there is a δ-regular graph with n vertices. Hence, the unique graphs in H(n,δ) that minimize the eMα2 index are the δ-regular graphs.

    If δn is odd, then handshaking lemma gives that there is no regular graph. Hence, there exists a vertex w with dwδ+1. Since duδ for every uV(G), handshaking lemma gives 2m(n1)δ+δ+1=nδ+1. We have

    eMα2(G)=uN(w)e(dudw)α+uvE(G),u,vwe(dudv)αuN(w)eδα(δ+1)α+uvE(G),u,vweδ2α.

    From the above and since w has at least δ+1 neighbors we have

    eMα2(G)(δ+1)eδα(δ+1)α+(mδ1)eδ2α,

    now using 2mnδ+1, we have

    eMα2(G)(δ+1)eδα(δ+1)α+(nδ+12δ1)eδ2α=(δ+1)eδα(δ+1)α+12(δ(n2)1)eδ2α,

    and equality in the bound is attained if and only if du=δ for every uV(G){w}, and dw=δ+1. Lemma 2.3 gives that there is a (δ+1,δ)-pseudo-regular graph with n vertices. Therefore, the unique graphs in H(n,δ) that minimize the eMα2 index are the (δ+1,δ)-pseudo-regular graphs.

    In [23,Theorem 2.1] appears the inequality

    eABC(G)Δ(e2(Δ1)Δe11Δ)+meABC(G)m.

    The equality holds in this bound if and only if G is a disjoint union of isolated edges or each connected component of G is a path graph Pk (k3) or a cycle graph Ck (k3).

    Proposition 3.1. If G is a graph with size m, then

    eABC(G)meABC(G)m.

    The equality holds if every edge of G is incident to a vertex of degree 2, or G is regular or biregular.

    Proof. ABC(G)=uvE(G)(du+dv2dudv). Note that the exponential function exp(x)=ex is a strictly convex function, and Jensen's inequality gives

    exp(1muvE(G)du+dv2dudv)1muvE(G)edu+dv2dudv,

    and the equality in this bound is attained if and only if du+dv2dudv=dw+dz2dwdz for every uv,wzE(G).

    If every edge of G is incident to a vertex of degree 2, then du+dv2dudv=12 for every uvE(G). If G is a regular or biregular graph, then du+dv2dudv=Δ+δ2Δδ for every uvE(G).

    Since 2(Δ1)Δ<11Δ if Δ>2, Propostion 3.1 improves [23,Theorem 2.1].

    The following result relates the exponential generalized atom-bound connectivity indices with positive and negative parameters.

    Theorem 3.2. Let G be a graph with m edges, minimum degree δ, maximum degree Δ>2, and without isolated edges, and let α,βR with α>0>β. Then

    e((2(Δ1)Δ2)α(2(Δ1)Δ2)β)eABCβ(G)eABCα(G),

    and the equality holds if and only if G is regular.

    If δ=1, then

    eABCα(G)e((11Δ)α(11Δ)β)eABCβ(G),

    and the equality holds if and only if G is the disjoint union of star graphs K1,Δ.

    If δ2, then

    eABCα(G)e((2(δ1)δ2)α(2(δ1)δ2)β)eABCβ(G).

    If δ>2, then the equality holds if and only if G is regular. If δ=2, then the equality holds if and only if each edge in G is incident to a vertex with degree two.

    Proof. For each fixed α and β with α>0>β, we are going to compute the extremal values of the function g:[δ,Δ]×[max{2,δ},Δ] (with Δ3) given by

    g(x,y)=e(x+y2xy)αe(x+y2xy)β=e((x+y2xy)α(x+y2xy)β).

    We have

    gx=e((x+y2xy)α(x+y2xy)β)(α(x+y2xy)α1β(x+y2xy)β1)1x2(2y1)0.

    Then the function g(x,y) is decreasing on x[δ,Δ] for each fixed y[max{2,δ},Δ] and consequently

    g(Δ,y)g(x,y)g(δ,y).

    Let us define

    g1(y)=g(Δ,y)=e((y+Δ2Δy   )α(y+Δ2Δy   )β).

    We have

    g1(y)=e((y+Δ2Δy   )α(y+Δ2Δy   )β)×(α(y+Δ2Δy)α1β(y+Δ2Δy)β1)1y2(2Δ1)<0.

    Then g1(y) is strictly decreasing, and consequently g1(Δ)g1(y). Therefore, for each uvE(G) we have

    e((2(Δ1)Δ2   )α(2(Δ1)Δ2   )β   )e(du+dv2dudv   )αe(du+dv2dudv   )β,e((2(Δ1)Δ2   )α(2(Δ1)Δ2   )β   )e(du+dv2dudv   )βe(du+dv2dudv   )α,e((2(Δ1)Δ2   )α(2(Δ1)Δ2   )β   )eABCβ(G)eABCα(G),

    and the equality in the last inequality holds if and only if du=dv=Δ for each uvE(G), i.e., G is a regular graph.

    Let us define

    g2(y)=g(δ,y)=e((y+δ2δy   )α(y+δ2δy   )β).

    We have

    g2(y)=e((y+δ2δy   )α(y+δ2δy   )β)×(α(y+δ2δy)α1β(y+δ2δy)β1)1y2(2δ1).

    If δ=1, then g2(y)>0 and so, g2(y) is strictly increasing. Consequently, g2(y)g2(Δ), and we have for each uvE(G)

    e(du+dv2dudv   )αe(du+dv2dudv   )βe((11Δ   )α(11Δ   )β),e(du+dv2dudv   )αe((11Δ   )α(11Δ   )β)e(du+dv2dudv   )β,eABCα(G)e((11Δ   )α(11Δ   )β)eABCβ(G),

    and the equality in the last inequality holds if and only if du=1 and dv=Δ o viceversa for each uvE(G), i.e., G is the disjoint union of star graphs K1,Δ.

    If δ=2, then g2(y)=0 and so, g2(y) is a constant function. We have

    g(x,y)g(2,y)=g2(y)=e((12   )α(12   )β)=e((2(δ1)δ2   )α(2(δ1)δ2   )β),e(du+dv2dudv   )αe(du+dv2dudv   )βe((2(δ1)δ2   )α(2(δ1)δ2   )β),e(du+dv2dudv   )αe((2(δ1)δ2   )α(2(δ1)δ2   )β)e(du+dv2dudv   )β,eABCα(G)e((2(δ1)δ2   )α(2(δ1)δ2   )β)eABCβ(G),

    and the equality in the last inequality holds if and only if each edge in G is incident to a vertex with degree two.

    If δ>2, then g2(y)<0 and so, g2(y) is strictly decreasing. Consequently, g2(y)g2(δ), and we have for each uvE(G)

    e(du+dv2dudv   )αe(du+dv2dudv   )βe((2(δ1)δ2   )α(2(δ1)δ2   )β),e(du+dv2dudv   )αe((2(δ1)δ2   )α(2(δ1)δ2   )β)e(du+dv2dudv   )β,eABCα(G)e((2(δ1)δ2   )α(2(δ1)δ2   )β)eABCβ(G),

    and the equality in the last inequality holds if and only if du=dv=δ for each uvE(G), i.e., G is a regular graph.

    The hypothesis Δ>2 in Theorem 3.2 is not an important restriction: If Δ=2, then G is is the disjoint union of path and cycle graphs with three or more vertices, and we have eABCα(G)=me(12)α. Hence,

    eABCα(G)=e((12)α(12)β)eABCβ(G).

    We have studied some properties of the generalized exponential indices. For the exponential index eMα2 with α>0, we characterize the graphs with extreme values in the class of graphs with a fixed number of vertices and in the class of graphs with a fixed minimum degree and a fixed number of vertices.

    In addition, we found some optimal inequalities involving the exponential atom-bound connectivity index. In particular, we found a bound that improves a result in [23]. Also, we obtained an inequality concerning the indices eABCα for different values of the parameter.

    As an open problem it remains to find the extremal graphs and to obtain optimal bounds for other generalized exponential vertex-degree-based topological indices. In particular, for the index eMa2 to find the extremal graphs in other classes, for example the class of graphs with n vertices and fixed maximum degree.

    This research is supported by a grant from Agencia Estatal de Investigación (PID2019-106433GB-I00 / AEI / 10.13039/501100011033), Spain.

    The author declare there is no conflict of interest.

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