Tanissia Djemai
email: tanissia.djemai@irit.fr

Patricia Stolf
email: patricia.stolf@irit.fr

Thierry Monteil
email: monteil@laas.fr

Jean-Marc Pierson
email: jean-marc.pierson@irit.fr

Mobility Support for Energy and QoS aware IoT Services Placement in the Fog

Keywords: Internet of Things, Optimization, Mobility, Fog Computing, Smart Campus, QoS, Energy

Fog computing has emerged as a strong distributed computation paradigm to support applications with stringent latency requirements. It offers almost ubiquitous computation capacities over a large geographical area. However, Fog systems are highly heterogeneous and dynamic which makes services placement decision quite challenging considering nodes mobility that may decrease the placement decision quality over time. This paper proposes a Mobility-aware Genetic Algorithm (MGA) for services placement in the Fog which aims at supporting nodes' mobility while ensuring both infrastructures energy-efficiency and applications Quality of Service (QoS) requirements. We have compared this approach with two variants of Shortest Access Point migration strategy (SAP) from the literature, a proposed Mobility Greedy Heuristic (MGH) and a baseline Simple Genetic Algorithm (SGA). Experiments conducted with MyiFogSim simulator have shown that MGA ensures good performances in terms of energy and delay violations minimization compared to other methods.

I. INTRODUCTION

Fog computing is a distributed computation paradigm that extends cloud infrastructures with computation and storage capabilities of nodes located between end users and data centers [START_REF] Bonomi | Fog Computing and Its Role in the Internet of Things[END_REF]. It supports latency-constrained applications, by hosting services and data as close as possible to end-users and leads to cloud-network traffic reduction . In the context of Internet of Things (IoT), the Fog infrastructure, composed by constrained computation and communication nodes, has to deal with a significant number of mobile IoT objects. Those objects may request at any time applications with heterogeneous computation and communication needs and context-usage priorities. Placing those applications considering the system dynamic induced by nodes mobility is quite challenging and needs to be addressed to ensure and maintain the Quality of Service (QoS) of applications over time. Moreover, the distributed and large-scale characteristics of IoT and Fog environments lead to a non negligible impact on energy consumption [START_REF] Iea | Energy Efficiency of the Internet of Things[END_REF] that should be considered as a prime parameter for any Fog-IoT services placement framework.

Mobility support has mainly been investigated with handover/handoff mechanisms and migration process, [START_REF] Wang | Dynamic Service Migration in Mobile Edge Computing Based on Markov Decision Process[END_REF], [START_REF] Aissioui | On Enabling 5G Automotive Systems Using Follow Me Edge-Cloud Concept[END_REF], defined respectively as the process of managing the connectivity of users between network cells and virtual services transfer from one computing node to another. Managing the mobility of nodes with migration induces many questions such as: "When the migration should start?", "Where to place services?" and "How to choose the data transfer path?". The migration process undeniably induces an extra processing time, network usage and energy consumption. Furthermore, if the requested IoT applications are designed in a distributed manner and hosted by different data-dependent virtual entities, it will be necessary to choose which and how services should be migrated to ensure the communication between them during the migration. In order to avoid the migration process and its previous cited drawbacks, this paper proposes a Mobility-aware Genetic Algorithm (MGA) and a Mobility Greedy Heuristic (MGH) as placement methods that consider mobility patterns of nodes while minimizing the infrastructure energy consumption and ensuring the QoS of applications. The contributions of this work can be summarized as follows:

(1) A probabilistic Genetic Algorithm and a greedy heuristic approaches for IoT-Fog services placement with nodes mobility support. [START_REF] Minh | Toward service placement on Fog computing landscape[END_REF] Performance comparison between different services placement approaches. The metrics considered are energy consumption and applications delay violations.

(3) An extension of MyiFogSim simulator that integrates some literature mobility patterns. The remainder of this paper is structured as follows : In Section II the state of the art of Mobility and Fog computing services placement is addressed. Section III gives the motivating scenario and a formalization of the placement problem. Section IV details the proposed placement methods. Finally, Section V reports experimental results using MyiFogSim.

II. RELATED WORK

Fog-Services placement problem has been widely investigated within a static Fog context (without mobility).

Fog and services placement problem in a static environment: Services placement problem in the Fog is commonly defined as an optimization problem to ensure one or multiple system QoS requirements such as response time, resource usage efficiency, network consumption minimization. For this purpose, different approaches have been used such as evolutionary optimization, various heuristics and exact resolutions under different system constraints [START_REF] Minh | Toward service placement on Fog computing landscape[END_REF], [START_REF] Skarlat | Optimized IoT service placement in the fog[END_REF], [START_REF] Canali | Genetic Algorithms for Service Placement in Fog Computing Systems[END_REF], [START_REF] Brogi | Meet Genetic Algorithms in Monte Carlo: Optimised Placement of Multi-Service Applications in the Fog[END_REF], [START_REF] Nardelli | Efficient Operator Placement for Distributed Data Stream Processing Applications[END_REF], [START_REF] Guerrero | A lightweight decentralized service placement policy for performance optimization in fog computing[END_REF]. Those works focus only on QoS requirements in a static Fog environment.

Fog and Energy: Authors in [START_REF] Liu | Multiobjective Optimization for Computation Offloading in Fog Computing[END_REF] try to minimize mobile nodes energy consumption, time and execution costs by transferring their tasks to complementary computation devices. This approach can induce to an excessive usage of bandwidth and increases the energy consumption of other nodes. Work in [START_REF] Mebrek | Efficient green solution for a balanced energy consumption and delay in the IoT-Fog-Cloud computing[END_REF] addresses the IoT to Fog nodes assignment problem with Genetic Algorithm (GA) and Broadcast Incremental Power (PIP) algorithm to reduce mobile nodes energy consumption under delay constraints. The approach does not consider the energy consumption of Fog, cloud nodes and the network. In [START_REF] Djemai | A Discrete Particle Swarm Optimization Approach for Energy-Efficient IoT Services Placement Over Fog Infrastructures[END_REF], authors use a Discrete Particle Swarm Optimization approach to minimize the infrastructure energy consumption and applications delay violations in a static Fog environment.

Fog and Mobility support: Although mobility is a key point to consider in the Fog, only few works investigate it. Authors in [START_REF] Bittencourt | Mobility-Aware Application Scheduling in Fog Computing[END_REF] consider the influence of nodes mobility for applications scheduling problem; however, the mobility information is not used by the algorithms and the mobility scenario is only based on increasing and decreasing the number of connected nodes and does not consider any mobility model. Authors in [START_REF] Mouradian | Application Component Placement in NFV-Based Hybrid Cloud/Fog Systems With Mobile Fog Nodes[END_REF] propose an Integer Linear Program to minimize applications makespan while considering a random way point mobility model. This model neglects the temporal and spatial aspects that define most of IoT nodes motion. In [START_REF] Cziva | Dynamic, Latency-Optimal vNF Placement at the Network Edge[END_REF], authors propose to dynamically re-schedule the placement of Virtual Network functions (VNF) to minimize end-to-end latency of users and the number of migrations. Compared to our work, this approach is only based on latency violation metric. None of these works introduces the mobility information in the placement modeling and algorithm.

III. SYSTEM DESCRIPTION AND PROBLEM STATEMENT

This section gives details about the considered scenario, the system model and the problem formulation.

A. Motivating Scenario, Assumptions and Mobility Model

We consider a Smart Campus area with pedestrians carrying IoT nodes that request applications and interact with their sensors and actuators. For instance, a smartphone can request for an augmented reality (AR) application. The processing services of the application will interact with the camera of the smartphone as a source sensor and consider the smartphone screen as the actuator. We aim to place the AR services considering the mobility of pedestrians.

For sake of simplicity, but without loss of generality, we make the following assumptions: (1) We consider a time-slotted system T = {t 0 , t 1 , .., t T -1 }. One slot duration is defined as half the time taken by the fastest node in the system to cross the shortest distance between two points and that one node movement is negligible within one slot i.e. one node can only change position at the beginning of a time t i . (2) We suppose that the service duration is infinite and that if two IoT user nodes1 u 1 and u 2 request the same application a 1 , each node will have its own virtual instances (i.e instances are not shared between two IoT nodes). (3) Following 5G specifications, we assume that a user u will always be under network coverage and it will be attached to one and only one access point at each time t ∈ T. [START_REF] Iea | Energy Efficiency of the Internet of Things[END_REF] We assume that communications between IoT users nodes and their services are uniformly distributed within the time window W T , that represents the studied time interval of T slots.

In environment that involves humans, mobility patterns are not as uncertain as in other systems. Moreover, with access technologies such as 5G and existing 4G-LTE , we may not need a precise location of nodes to ensure good services and mobility management. In our approach, we use the Weighted Waypoints mobility model (WWP) that considers location, pause duration and weights to choose the next destination place. It has been built from a mobility survey carried out on the campus of the University of Southern California. The WWP defines a set of locations called waypoints. The probability that mobile nodes move from waypoint a to waypoint b depends on current location and time [START_REF] Hsu | Weighted waypoint mobility model and its impact on ad hoc networks[END_REF].

B. System Representation 1) Physical topology:

We consider a hierarchical Fog infrastructure described by an non directed graph G = (M, L) and shown in Figure 1, where M is the set of nodes, and L the set of direct links between them.

Each physical node m k ∈ M is defined by: (1) a type η k ∈ {IoT, F og, Cloud} (2) a capacity vector

Ω k =< cpu max k , ram max k , disk max k >,
t k = 0. Each network link l (k,k ′ ) ∈ L between nodes m k and m k ′ is defined with its bandwidth bw (k,k ′ ) in (Mb/s) and latency lc (k,k ′ ) in (ms). l (k,k ′ ) can be one direct link from m k to m k ′
or be composed by several links.

2) Internet of Things applications: We consider a set of IoT applications A = {a 0 , .., a i , .., a A-1 } designed in a distributed manner. Each application a i ∈ A has a class type Υ which can be: Mission Critical (MC), Real Time (RT), Streaming (ST) and Best Effort (BE), having respectively priority level ψ of 0, 1, 2, and 3 and response delay requirement φ of 20ms, 50ms, 150ms and ∞, details are given in [START_REF] Djemai | A Discrete Particle Swarm Optimization Approach for Energy-Efficient IoT Services Placement Over Fog Infrastructures[END_REF].

An application a i has a set of size n i of communicating data-dependent services represented with a directed graph G(a i ) = (S ai , E ai ). Each service s j ∈ S ai is defined by its requested CPU mi j (MIPS) and RAM ram j (MB), deployment technology tec j (either a virtual machine, a container, OSGi plugin, Java Virtual Machine or a combination of them). We consider two specific nodes in the graph G(a i ) that represent respectively sensor sending service (source node) and actuator receiving service (sink node).

Each directed edge e (j,j ′ ) ∈ E ai , from service s j to service s j ′ represents a data dependency between s j and s j ′ and carries data (j,j ′ ) , the volume of data sent from s j to s j ′ in (KB). We would like to draw the reader's attention to the fact that we have willingly ignored the application index i while using the notation s j rather than s ij to lighten the model.

C. Problem Formulation and Objective Function

We consider a set of mobile IoT nodes U requesting a set of applications A t0 at initial time t 0 . Each IoT node u ∈ U has a set A t0 u of requested applications and N t0 u , the set of all services in A t0 u . Let's consider the binary decision variable x u jk equals to 1 if service j ∈ N t0 u requested by node u is placed on node k and equals to 0 otherwise. The first metric we consider, defined in Eq (1), is the sum of computation and network energy consumption during T time slots. As the energy model does not impact our resolution approach, we have chosen, similarly to work [START_REF] Beloglazov | Energy-aware resource allocation heuristics for efficient management of data centers for Cloud computing[END_REF] a linear model, but other models could be used [START_REF] Xu | Stochastic Modeling and Analysis with Energy Optimization for Wireless Sensor Networks[END_REF].

f1 = fC + fN (1)
The computation part is estimated according to the following equation:

fC = T u∈U j∈Nu k∈M x u jk α u jk γ c k (2)
α u jk is the computation time of service instance j associated to the IoT user node u and placed on node k as defined in Eq (3). As the placement is made at the beginning and will remain unchanged, the computation cost is time independent. Placing service j on node k depends on the maximum processing capacity of the physical node cpu max k in MIPS, the amount of MIPS allocated to other services placed on the machine k and the amount of requested MIPS of service j. . The communication part is estimated according to the following equation:

fN = z∈M-u,t∈T P t uz j,j ′ ∈Nu k,k ′ ∈M x u jk x u j ′ k ′ β ut jj ′ ,kk ′ γ n kk ′ (4)
β ut jj ′ ,kk ′ defines the communication time between service instances j and j ′ placed respectively on nodes k and k ′ at time t for user node u. In contrast to the computation time, the communication time β ut jj ′ ,kk ′ varies over time, because it is impacted by the fluctuation of latency between the mobile node and its processing services placed on the infrastructure. There are two possible causes for this fluctuation : (1) The IoT node does not host services; then the latency variation is due to the communication between sensors and their destination services and actuators and their source services. (2) The IoT node hosts services; then the communication latency between those services and other services will vary over time depending on the localization of the IoT node's.

β ut jj ′ ,kk ′ = 1 T data (j,j ′ ) bw t (k,k ′ ) + lc t (k,k ′ ) (5)
γ n kk ′ is the communication power constant between node k and node k ′ and is defined by γ n kk ′ = P n max k

+ P n max k ′ - P n min k -P n min k ′
, where P n max and P n min are respectively the maximum and minimum power consumption of nodes network interfaces.

P t uz is the probability that an IoT node u is under the coverage zone of a Fog node z at time t. Its computation varies according to the chosen mobility model. This work considers the Weighted Waypoints Model (WWP). Considering a set of Waypoints and Access points located in a 2D area, we compute the Euclidean distance between each waypoint and Access point. Then, under the assumption that each waypoint is attached to one and only one Access point, we associate Waypoints to their closest Access point. P t ur is the probability that user u will be in waypoint r at time t and is equal to P uz previously defined. P t uz = P t ur .

2) Delay violations :

The second considered metric is the QoS violation metric defined in Eq (6) by the average number of applications delay violations.

f2 = 1 T u∈U a∈A w t a (u) (6)
where w t a (u) is equal to 1 if the application response delay d t a (u) is greater than its maximum delay requirement D a . Otherwise it is equal to 0. The maximum response delay D a of the application a varies according to its class type Υ as presented in III-B. The estimated response delay d t a (u) corresponds to the time between the sending of one data packet from the sensor of node u and its corresponding action on the actuator. The delay depends on the position of the IoT nodes and the placement of the used services. For each instance of the application a ∈ A requested by an IoT user node u ∈ U, we compute the d t a (u) according to the possible position of the user at time t as follows:

d t a (u) = j∈Nu k∈M x u jk α u jk + z∈M-{u} P t uz j,j ′ ∈N k,k ′ ∈M x u jk x u j ′ k ′ β jj ′ ,kk ′ (7)
3) Objective function: We combine considered the objectives into a single function, defined in Eq [START_REF] Djemai | A Discrete Particle Swarm Optimization Approach for Energy-Efficient IoT Services Placement Over Fog Infrastructures[END_REF], to have Mono-objective (MAM) optimization approach which is recommended in many works such as [START_REF] Chamas | Two-phase virtual machine placement algorithms for cloud computing: An experimental evaluation under uncertainty[END_REF], instead of computing the Pareto front that could be time consuming. We aim to find a solution that is a trade-off between the two objectives and gives a little advantage to the energy aspect.

F = f1(1 + f2) (8)
IV. PLACEMENT ALGORITHMS A. Mobility-aware Genetic Algorithm (MGA) Genetic Algorithm (GA) is an evolutionary based optimization approach, efficiently used for NP-hard problems resolution [START_REF] Liu | An energy-efficient virtual machine placement algorithm in cloud data center[END_REF]. It has shown its efficiency in static Fog environments placement problems [START_REF] Canali | Genetic Algorithms for Service Placement in Fog Computing Systems[END_REF]. We propose to apply the GA method with a probabilistic objective function enhanced by nodes mobility information. A chromosome c, is a vector representing the placement solution. Each vector element is indexed by the service Id s u j and gives the node Id m k that will host the service. IoT users nodes are sorted by the increasing number of requested applications. The applications of each user node are sorted by the increasing priority values, and services of each application are sorted by increasing CPU demand. Through experiments we have chosen the following parameters values: mutation rate λ = 0.01, crossover rate σ = 0.8, population size P = 20, number of generations µ = 20 and a 1-way tournament selection. The fitness of chromosomes is computed according to Eq [START_REF] Djemai | A Discrete Particle Swarm Optimization Approach for Energy-Efficient IoT Services Placement Over Fog Infrastructures[END_REF] where the mobility model is used. For each user node u that requested an application at time slot t 0 and for each time step t ∈ T of the time window, we get the mobility information of u. The mobility information P t uk is the probability that the user node u is under the coverage zone of Fog node k. MGA is presented in Pseudo Algorithm (1).

Algorithm 1 Mobility-aware Genetic Algorithm (MGA) for IoT service placement

Get mobility information for each mobile node that has requested an application at time t0. Generate uniformly the initial population of size P and compute the fitness value for each chromosome with Eq [START_REF] Djemai | A Discrete Particle Swarm Optimization Approach for Energy-Efficient IoT Services Placement Over Fog Infrastructures[END_REF]. while The number of generations µ is not reached do while Next generation population size does not reach σP individuals do On (100 * σ)% of the population apply 1-way tournament selection to select a pair of parents chromosomes c1, c2.

Apply Crossover operation on c1, c2 to get a resulting new chromosome c3 by taking first genes from c1 and the rest from c2.

Apply mutation operation on c3 with probability λ.

Compute fitness of c3 according to Eq [START_REF] Djemai | A Discrete Particle Swarm Optimization Approach for Energy-Efficient IoT Services Placement Over Fog Infrastructures[END_REF] where the probabilistic part related to mobility is detailed in Eq (4). Put c3 in the next generation population end while Keep (100 * (1 -σ))% of the best individuals from the previous population and add them to the new generation population. Increment the number of generations (µ value). end while=0

B. Mobility Greedy Heuristic (MGH)

The main idea of the MGH heuristic is to consider the most probable path for each mobile device and then compute the placement that will reduce the energy consumption and communication delay based on those paths. MGH steps are as follows: (1) The most probable path is composed greedily by taking the next position that has the highest probability value within the transition matrix of the WWP model. (2) User nodes are sorted by increasing number of applications demand and then services within each application are sorted first by data dependency (within sensor to actuator data path), and second by increasing CPU demand. (3) For each time t ∈ T , user u ∈ U, application a i ∈ A u , we try to place s j ∈ a i . We estimate system computation energy consumption f C , communication time d t a and communication energy consumption f N of the sub-graph composed of previous placed services and the service s j . The computed values of f C ,f N and d t a are normalized and then the chosen placement is the one that gives the minimum value of

G = 1 T (f C + f N + d t a
). The placement of s j is never reconsidered when placing the remaining services. MGH has a different fitness formula from MGA one but it has same objectives : minimize delay violations and energy consumption. MGA approach places services of all applications at the same time, so it is possible to estimate delay violations in the set of applications. In contrast, the MGH places services gradually and for each new service to place it tries to minimize greedily the communication delays between this last and previous placed services. V. EVALUATION

A. Experimentation description

For the validation of our placement approaches, we propose a Fog infrastructure deployed in a 18Km 2 square geographical area, represented in Figure 2 and simulated with Myi-FogSim [START_REF] Lopes | Myi-FogSim: A Simulator for Virtual Machine Migration in Fog Computing[END_REF]. Experiments have been conducted on an Intel Core i5-7200U CPU @ 2.50GHz x 4. MyiFogSim has been extended to allow the integration of various mobility models. As it is shown in Figure 2 from section III-A, the computing infrastructure is composed of fixed-located Fog nodes at each waypoint in the mobility layer. Fog nodes are connected to the cloud with wireline links and they are reachable by IoT nodes via access point devices. Nodes capacities values are taken uniformly within intervals specified in Table I. Each IoT node (smartphone) requests an application chosen uniformly within applications class set defined in Section III-B2. Each application a i has a services set size of n i = 3 and its graph is either modeled with a Sequential Unidirectional or a Master Slave data flow processing graphs with one sensor as data source and one actuator as sink. The graphs are represented in Figure 3. Service demand in terms of processing, memory and storage are taken from applications presented in [START_REF] Mahmud | Modelling and Simulation of Fog and Edge Computing Environments using iFogSim Toolkit[END_REF]. The time window W T is composed of T homogeneous time slots. At t 0 , IoT nodes request their applications (one application per IoT node). For the mobility aspect, we consider several pedestrians carrying smartphones moving between five waypoints in the campus according to the Weighted Waypoints model. The considered waypoints are: "Classroom", "Library", "Cafeteria", "Other area on the campus", "Off campus area". Pause time distributions and transition for each waypoint and transition matrices are detailed in [START_REF] Hsu | Weighted waypoint mobility model and its impact on ad hoc networks[END_REF]. At t 0 , IoT mobile nodes are uniformly distributed between the waypoints. We compare the proposed placement methods with a Simple Genetic Algorithm (SGA) and with two other strategies using migration from the literature (SAP and K-SAP). (3) K-Users Shortest Access Point migration Server (K-SAP) consists of applying SAP migration process for K mobile nodes chosen randomly. For the other nodes, services will remain placed on Fog nodes associated to their closest Access point at t 0 . The minimum value of parameter K is 0 and gives us a non migration strategy (a static placement based on initial position of nodes). The maximum value of K is the maximum number of mobile nodes and leads the K-SAP to act as the SAP strategy. After conducting experiments with various values of K we have chosen to present the most advantageous configuration for K-SAP which is K equal to 50% of IoT users nodes. We set the time window W T to 1000 * 60 * 30 with a time slot duration of 1000 * 60 * 5 respectively equivalent to 30 minutes and 5 minutes. We vary uniformly the characteristics of nodes according to values in Table I 10 times. For each infrastructure configuration we vary IoT nodes size from 2 to 100. For each infrastructure configuration and IoT nodes size, we vary mobility seeds 30 times. For each infrastructure configuration, IoT nodes size and mobility seed, we vary the characteristics of applications 30 times with priority values and maximum response delay taken uniformly within values given in Section III-C, graphs are taken uniformly between Maser-Slave and Sequential unidirectional processing data flow. Computation and storage demands of services are taken from [START_REF] Mahmud | Modelling and Simulation of Fog and Edge Computing Environments using iFogSim Toolkit[END_REF]. Presented results are the average values by IoT nodes size experiment. We would like to draw the reader's attention to the fact that those experiments focus on the mobility aspect of IoT nodes and the placement of their associated services. For this reason, the dimension of the problem that is increased is the number of IoT nodes and consequently the number of requested application.

B. Results

a) Impact of number of IoT nodes on computation energy: Figure 4a plots the average computation energy consumption f C in joules by increasing number of mobile nodes for each placement method. We observe that both MGA and SGA methods minimize the computation energy consumption and give similar results. The energy consumption due to the services computation is not impacted by nodes mobility: services are still hosted by the same machine during nodes movements. These algorithms give better results than MGH, SAP and K-SAP, the latter two giving similar results which are the worst. The migration process in SAP and K-SAP increases the energy computational cost because it uses VMs replica to ensure services continuity for the IoT nodes. Moreover, those strategies aim at reducing latency between services and mobile nodes and do not consider the energy cost. Also, K-SAP is less efficient compared to MGA and SGA, due to its greedy logic for choosing a host to place a service (it does not reconsider the placement decision for previous placed services).

b) Impact of number of IoT nodes on communication energy: Figure 4b plots the communication energy consumption f N of the infrastructure in joules by increasing number of mobile nodes for each placement method. In contrast to the previous Figure 4a and as expected, the SAP approach, which migrates the services following nodes paths, gives the lowest communication energy, followed by MGA. By avoiding the migration process, MGA gives as good results as migration strategies while minimizing communication energy consumption. The MGA reduces in average, for all problem size (IoT nodes set size), communication energy consumption by 73%, 55% and 93% compared respectively to K-SAP, SGA and MGH, while SAP outperforms MGA by less than 20%. K-SAP approach is less efficient because it migrates only K nodes services. In this scenario the network cost due to migrations is less important than the network cost due to communications between IoT nodes and their services. SGA method is less efficient to minimize this metric because it takes only the initial position of IoT nodes as input.

c) Impact of number of IoT nodes on delay violations: Figure 4c shows the average number of delay violations f 2 for different number of IoT mobile nodes for each placement approach. We notice that SAP gives the lowest delay, followed by MGA, MGH and SGA (the latter giving similar results). At each slot t, SAP migrates initial services directly on the closest Fog server which minimizes at each slot t the delay between mobile node and its services and reduces in average, for all problem sizes, delay violations by 48% compared to MGA. K-SAP, by migrating only services for half mobile nodes and keeping others on the initial nodes (the closest Fog server), gives worse results. MGA is as good as K-SAP with an average reduction of violations by 0.68% compared to K-SAP, which is due to its probabilistic mobility-based approach for delay violations minimization. MGA also reduces the number of violations by 28% and 29% compared respectively to SGA and MGH. d) Impact of number of IoT nodes on execution time of the placement method: Figure 5b shows the average computation time of MGA, SGA and MGH methods. MGH is a fast greedy method compared to SGA and MGA which are both evolutionary algorithms and usually those techniques are more time consuming compared to greedy heuristics. Moreover, MGA has an additional computation time compared to SGA which is due to mobile nodes paths estimation. Nevertheless, we notice that MGA takes only 6 seconds to place 270 services (3x90) in an infrastructure containing 90 mobile nodes. In this figure we present the time taken by the placement approaches to choose a services placement combination that minimizes the previously defined objectives. K-SAP and SAP are migration approaches, so their computation time is not comparable with the computation time of the described placement strategies.

e) Results analysis: migration strategy to minimize delay violations. From the previous analyzed results, we can conclude that the MGA gives a good trade-off between both energy and delay violations values and gives better results than some migration strategies.

The MGA strategy can be considered as a good alternative to avoid migration operations that can be time and energy consuming approaches. MGA offers a new way to handle dynamic environments with mobile nodes.

VI. CONCLUSION

In this work we have presented a probabilistic mobilitybased Genetic Algorithm (MGA) and a mobility greedy heuristic (MGH) for an efficient services placement in the Fog that minimizes the infrastructure energy consumption and applications delay violations over time. We have extended MyiFogSim with mobility models and implemented a pedestrian mobility scenario in a smart campus with a Weighted Waypoints mobility model [START_REF] Hsu | Weighted waypoint mobility model and its impact on ad hoc networks[END_REF]. The proposed placement method MGA, outperforms the migrations strategies SAP and K-SAP for energy minimization and it outperforms SGA, K-SAP and MGH for delay violations minimization. As future work, we will extend our model with vehicles mobility models and study the scalability of the proposed approaches by increasing the number of application services, since preliminary experiments have shown that it does not impact significantly the approaches performances. We plan to work with various applications topologies to investigate their impact on the placement approaches behaviors.

VII. ACKNOWLEDGMENT

This work is supported by neOCampus project, Toulouse university, France.

Fig. 1 .

 1 Fig. 1. Physical Topology representation highlighting the system's variables

  α u jk = mij + u∈U l∈N u -{j} mi l x u lk cpu max k (3) γ c k is the computation power of node k: It represents the difference between node maximum and minimum power consumption γ c k = P c max k -P c min k

Fig. 2 .Fig. 3 .

 23 Fig. 2. Experiments map representing mobility and the Fog layers

  (1) Static Genetic Algorithm (SGA) has the same parameters values and fitness function as MGA but it does not consider the mobility model of IoT nodes. That means that for each IoT node u ∈ U, Fog node k ∈ M and time t ∈ T we have P t uk = P t0 uk . (2) Shortest Access Point migration Server Cloudlet (SAP) consists in placing initially the requested services on the Fog node which is associated to the IoT node closest Access point. Then at each time slot, those services are migrated to the distance-closest cloudlet (Fog node) following user's nodes path through Access points.

Fig. 4 .

 4 Fig. 4. Average energy consumption and delay violations per increasing number of IoT nodes for each placement approach

  parameters units of elements are respectively in MIPS, MB and MB. (3) a 2D coordinates and a coverage zone vector at time t, Nodes have additionally characteristics depending on their type: (1) IoT node: It has computation and storage capacities and a set of sensors H 0 k and actuators H 1 k components. IoT nodes move according to a probability mobility model ϑ k (e.g. Manhattan model) [16], and have a set of requested applications A t It has the ability to connect IoT nodes to external network through Access point equipment and has computation and storage capacity through a server cloudlet device. (3) Cloud node: It is defined as a limitless computation data center server. The coverage zone is fixed to r

	∆ t k =< x t k , y t k , r t k >.

k at time t ∈ T. The coverage zone is fixed to r t k = 0. Let U be the subset of M with only IoT nodes. (2) Fog node:

TABLE .

 .

					I.
			INFRASTRUCTURE NODES DETAILS
	Node Number	CPU	Interval	RAM Interval	Min-	Min-	Up
			(MIPS)		(MB)	Max	Max	Bandwidth
						CPower a	NPower b	Inter-
								val(GB/s)
	Cloud 1	[2400000, 9600000]	[25000, 100000] [320.339-	[60.21-	-
						120.43]	160.16]
	Fog	6	[1400000, 5600000]	[12500, 50000]	[107.339-	[41.7165-	[1,10]
						83.433]	53.66]
	IoT	[2, 100]	[500, 2000]		[512, 2948]	[87.53-	[41.22-	[1,10]
						82.44]	43.76]

a Computation Power, b Communication Power.

"IoT user node" or "user node" terms refer to a node that has requested an application and "node" term refers to any computation node that includes also the IoT nodes.


C Monticelli

A Balbo

J Esvan

C Chiavari

C Martini
email: carla.martini@unibo.it

F Zanotto

L Marvelli
email: lorenza.marvelli@unife.it

L Robbiola
email: robbiola@univ-tlse2.fr

Evaluation of 2-(salicylideneimino) thiophenol and other Schiff bases as bronze corrosion inhibitors by electrochemical techniques and surface analysis

Keywords:

In this research, different Schiff bases were synthesized and tested as bronze corrosion inhibitors in concentrated synthetic acid rain at pH 3.3. Some of them showed good inhibiting effects, as detected by EIS and polarization curve recording. The most efficient inhibitor (2-(salicylideneimino) thiophenol, SITP) was also tested with addition of sodium dihydrogen phosphate (P). P improved the surface film resistance against breakdown phenomena. XPS and SEM investigations showed that SITP and SITP + P significantly hinder decuprification. Moreover, SITP forms a protective layer on bronze, composed of both Cu(I)-SITP complexes and adsorbed inhibitor molecules. Cu(II) phosphates were also detected with P addition.

Introduction

Ancient and modern bronze artefacts are an important part of our cultural heritage and the development of effective protective treatments with no adverse effect on health and environment is still an unresolved issue. This research deals with the identification of new bronze corrosion inhibitors in concentrated synthetic acid rain and represents a first step in a more complex research activity, aiming at developing new non-hazardous protective coatings for outdoor bronze artefacts, entrapping corrosion inhibitors. In a subsequent step of this research, the most efficient substance will be encapsulated in the coatings with the aim to increase their long term protectiveness. Some preliminary results were presented in [START_REF] Monticelli | Entrapment of corrosion inhibitors in silane coatings to improve bronze corrosion protection[END_REF].

Up to now, the most efficient organic inhibitors of bronze corrosion have mainly been azoles and particularly triazoles [START_REF] Golfomitsou | Synergistic effects of corrosion inhibitors for copper and copper alloy archaeological artefacts[END_REF][START_REF] Rahmouni | The inhibiting effect of 3-methyl 1,2,4-triazole 5-thione on corrosion of copper in 3% NaCl in presence of sulphide[END_REF][START_REF] Degrigny | The methodology of the PROMET project to develop/ test new non-toxic corrosion inhibitors and coatings for iron and copper alloy objects housed in Mediterranean museums[END_REF], tetrazoles [START_REF] Golfomitsou | Synergistic effects of corrosion inhibitors for copper and copper alloy archaeological artefacts[END_REF][START_REF] Balbo | Effectiveness of corrosion inhibitor films for the conservation of bronzes and gilded bronzes[END_REF], imidazoles [START_REF] Marušić | Inhibiting effect of 4-methyl-1-ptolylimidazole to the corrosion of bronze patinated in sulphate medium[END_REF] and thiadiazoles [START_REF] Golfomitsou | Synergistic effects of corrosion inhibitors for copper and copper alloy archaeological artefacts[END_REF][START_REF] Balbo | Effectiveness of corrosion inhibitor films for the conservation of bronzes and gilded bronzes[END_REF][START_REF] Ying | Study on the inhibiting behavior of AMT on bronze in 5% citric acid solution[END_REF][START_REF] Do Lago | The use of experimental design for the study of the corrosion of bronze pretreated with AMT in artificial rainwater[END_REF]. The inhibition mechanism of these substances has been investigated above all on copper, as it is the main alloying element in bronze. Chemisorption was found to occur through the electron lone pairs in N atoms and/or through delocalized π-electrons in aromatic rings favoured by the concomitant presence of other heteroatoms with donor nature, like S, either in the ring or in functional groups [START_REF] Antonijević | Films formed on copper surface in chloride media in the presence of azoles[END_REF]. In acid solutions, azole adsorption is weak suggesting that it mainly occurs through the deprotonated molecular forms [START_REF] Cotton | Benzotriazole and related compounds as corrosion inhibitors for copper[END_REF][START_REF] Zucchi | Tetrazole derivatives as corrosion inhibitors for copper in chloride solutions[END_REF][START_REF] Subramanian | Effect of the adsorption of some azoles on copper passivation in alkaline medium[END_REF], except for molecules of very basic nature like imidazoles, which also adsorb significantly in the neutral form [START_REF] Kovačević | The relation between adsorption bonding and corrosion inhibition of azole molecules on copper[END_REF][START_REF] Kovačević | How relevant is the adsorption bonding of imidazoles and triazoles for their corrosion inhibition of copper?[END_REF][START_REF] Petrović Mihajlović | Imidazole based compounds as copper corrosion inhibitors in seawater[END_REF]. Whether azoles adsorb directly on copper metal [START_REF] Fang | A photoemission study of benzotriazole on clean copper and cuprous oxide[END_REF][START_REF] Tromans | Anodic Polarization Behavior of Copper in Aqueous Chloride/Benzotriazole Solutions[END_REF][START_REF] Tommesani | On the protective action of 1,2,3-benzotriazole derivative films against copper corrosion[END_REF] or on a surface cuprous oxide film is still under debate [START_REF] Antonijević | Films formed on copper surface in chloride media in the presence of azoles[END_REF][START_REF] Antonijević | Copper corrosion inhibitors. A review[END_REF][START_REF] Finšgar | Inhibition of copper corrosion by 1,2,3-benzotriazole: A review[END_REF]. Some authors couple the two theories and maintain that, after an initial step of direct adsorption on the metal surface, slow copper oxidation to Cu(I) proceeds and determines the subsequent growth of a polymeric Cu(I)-inhibitor film [START_REF] Xue | XPS and electroanalytical studies of the chemisorption of benzotriazole on a freshly etched surface and an oxidized surface of copper[END_REF][START_REF] Chen | Benzotriazole as a volatile corrosion inhibitor during the early stage of copper corrosion under adsorbed thin electrolyte layers[END_REF][START_REF] Bi | Some aspects of the role of inhibitors in the corrosion of copper in tap water as observed by cyclic voltammetry[END_REF], which most likely lies [START_REF] Modestov | A study of the electrochemical formation of Cu(I)-BTA films on copper electrodes and the mechanism of copper corrosion inhibition in aqueous chloride/benzotriazole solutions[END_REF][START_REF] Finšgar | Determination of the Cu 2 O thickness on BTAH-inhibited copper by reconstruction of Auger electron spectra[END_REF][START_REF] Finšgar | 2-Mercaptobenzoxazole as a copper corrosion inhibitor in chloride solution: electrochemistry, 3D-profilometry, and XPS surface analysis[END_REF] on a thin Cu 2 O inner layer. A 24 Å thick Cu(I)-BTA layer doped with Cu 2 O was found to grow on copper in neutral chloride solution after short immersion times [START_REF] Kosec | Impedance and XPS study of benzotriazole films formed on copper, copper-zinc alloys and zinc in chloride solution[END_REF].

In the field of bronze heritage conservation [START_REF] Golfomitsou | Synergistic effects of corrosion inhibitors for copper and copper alloy archaeological artefacts[END_REF][START_REF] Degrigny | The methodology of the PROMET project to develop/ test new non-toxic corrosion inhibitors and coatings for iron and copper alloy objects housed in Mediterranean museums[END_REF], BTA and triazole derivatives are the most commonly used inhibitors, even if toxicity concerns have been raised regarding BTA as a result of its leaching into the environment [START_REF] Pillard | Toxicity of benzotriazole and benzotriazole derivatives to three aquatic species[END_REF] and suspected carcinogenicity to humans [START_REF]Benzotriazole. Health-based Recommended Occupational Exposure Limit[END_REF].

Some substances, belonging to the class of Schiff bases and considered non-toxic to the environment [START_REF] Ma | Inhibition of copper corrosion by several Schiff ; bases in aerated halide solutions[END_REF], have been proven to be efficient inhibitors of copper corrosion in acidic and neutral solutions of chlorides [START_REF] Antonijević | Copper corrosion inhibitors. A review[END_REF][START_REF] Ma | Inhibition of copper corrosion by several Schiff ; bases in aerated halide solutions[END_REF][START_REF] Monticelli | The inhibitive action of some Schiff Bases and amines towards the corrosion of copper in an aqueous alcoholic medium[END_REF][START_REF] Quan | Adsorption behaviour of Schiff base and corrosion protection of resulting films to copper substrate[END_REF][START_REF] Ehteshamzade | Inhibition of copper corrosion by self-assembled films of new Schiff bases and their modification with alkanethiols in aqueous medium[END_REF]. They are claimed to produce thin protective layers on the metal surface, by forming N-Cu coordinate bonds or πelectron interactions with the surface Cu 2 O film [START_REF] Ma | Inhibition of copper corrosion by several Schiff ; bases in aerated halide solutions[END_REF]. The introduction of a thiol group into the molecular structure favours the inhibitor chemisorption on pure copper from hydroalcoholic solutions [START_REF] Monticelli | The inhibitive action of some Schiff Bases and amines towards the corrosion of copper in an aqueous alcoholic medium[END_REF].

In our laboratory, some Schiff bases were purposely synthesized and investigated as corrosion inhibitors of bronze during 480 h of immersion in concentrated synthetic acid rain. Since some phosphonates mixed with amine substances revealed a synergistic inhibition effect against steel corrosion [START_REF] Ochoa | The synergistic effect between phosphonocarboxylic acid salts and fatty amines for the corrosion protection of a carbon steel[END_REF], the onset of a similar synergistic inhibition effect was attempted by adding phosphate ions to the most efficient Schiff base (i.e. 2-salicylideneimine thiophenol, SITP). The composition and microstructure of the bronze substrate used during the tests were comparable to those of Renaissance bronze [START_REF] Balbo | Effectiveness of corrosion inhibitor films for the conservation of bronzes and gilded bronzes[END_REF]. When in contact with a concentrated synthetic acid rain, a patina which is very similar to those actually found on ancient bronze artworks develops [START_REF] Chiavari | Protective silane treatment for patinated bronze exposed to simulated natural environments[END_REF].

The mechanism of SITP corrosion inhibition, in the absence and presence of phosphate ions, wasstudied not only by electrochemical techniques, but also by scanning electron microscope associated with energy dispersive spectroscopy (SEM-EDS), Raman spectroscopy and Xray photoelectron spectroscopy (XPS). These techniques led to a better understanding of the influence of the inhibitor addition against bronze decuprification.

Experimental part

Specimens and aggressive environment

The specimens were cut from an as-cast bronze alloy sheet with composition (91.9 Cu, 2.4 Sn, 1.0 Pb, Zn 2.9, 0.8 Sb, wt.%) and microstructure reproducing those of Renaissance bronze artefacts with cored dendrites of Cu-solid solution with Sn-and Sb-local enrichment, also including Pb globules in the interdendritic spaces, as reported in previous papers [START_REF] Balbo | Effectiveness of corrosion inhibitor films for the conservation of bronzes and gilded bronzes[END_REF][START_REF] Chiavari | Protective silane treatment for patinated bronze exposed to simulated natural environments[END_REF][START_REF] Masi | X-ray Photoelectron Spectroscopy as a tool to investigate silane-based coatings for the protection of outdoor bronze: The role of alloying elements[END_REF].

Bronze electrodes were soldered to sheathed copper wires to ensure electrical connection for electrochemical tests and then embedded in epoxy, with an exposed surface area of 1 cm 2 . Before immersion in the aggressive solutions, the electrode surface was prepared by grinding with emery papers up to P 1000 grade and then polished with 1 μm diamond powder to a mirror finishing. Finally, they were degreased with ethyl alcohol and washed with deionized water.

The test solution consisted of a tenfold concentrated synthetic acid rain (pH 3.3) indicated as ARX10 and prepared according to the recipe reported in [START_REF] Chiavari | Atmospheric corrosion of fire-gilded bronze: corrosion and corrosion protection during accelerated ageing tests[END_REF]. In ARX10, the ion concentrations were: SO 4 2-19.0 mg L -1 , Cl-12.7 mg L -1 , NO 3 -46.2 mg L -1 , CH 3 COO-2.3 mg L -1 , HCOO-0.5 mg L -1 , NH 4 + 10.5 mg L -1 , Ca 2+ 3.4 mg L -1 , Na + 5.3 mg L -1 .

The solution temperature was 30 °C. The Schiff bases tested as corrosion inhibitors were 2-(salicylideneimino) thiophenol (SITP), 2-salicylideneimino) aminophenol (SIAP), 2 -(3-methoxy-salicylideneimino) thiophenol (MSITP), N,N'-O-phenylen-bis(3-methoxy-salicylideneimine) (PMSI) and [2-(2-thiophenyl) imino]-1,2-diphenylethanone (TPIE), with structural formulas reported in Fig. 1. They were synthesised starting from the corresponding amines and aldehydes in the Inorganic Chemistry Laboratory of the University of Ferrara and their purity was checked by elemental analysis, Fourier Transform Infrared (FTIR) spectroscopy and Proton Nuclear Magnetic Resonance ( 1 H NMR) technique. Given the low Schiff bases solubility, they were always tested as ARX10 solutions saturated at 30 °C and filtered. The saturation concentrations in ARX10 at 30 °C were 0.7 mM (in the case of SITP), 0.3 mM (SIAP, MSITP, PMSI) and 0.4 mM (TPIE).

The inhibiting efficiency of the most concentrated and most effective substance (SITP) was also evaluated in the presence of phosphate ions, added as sodium dihydrogen phosphate (NaH 2 PO 4 , henceforward indicated by the label P), at the concentration of 10 -2 M. The addition of P determined a negligible increase in solution pH compared to that of the ARX10 solution containing or not containing the Schiff bases (from 3.3 to 3.6). Reference tests were also carried out in ARX10 in the presence of only 10 -2 M P.

Electrochemical tests

Electrochemical tests were carried out in a conventional thermostated three-electrode cell using a EG&G potentiostat/galvanostat model 273 A, piloted by PowerSuite software. The reference and auxiliary electrodes were a saturated calomel electrode (SCE) and a Pt sheet, respectively. All the potential values quoted in the text refer to SCE. Three experiments were carried out under each experimental condition.

Electrochemical Impedance Spectroscopy (EIS) tests were performed at the open circuit potential during 480 h exposures to uninhibited and inhibited solutions by applying a voltage perturbation amplitude of 10 mV (rms) in the frequency range 10 4 -10 -3 Hz with 5 points per frequency decade. The spectra were fitted by SAI ZView v.3.5c software, according to the most suitable equivalent circuit, as described in the text.

Ohmic drop-compensated polarization curves were recorded after both 1 h immersion and at the end of the 20 days of immersion in uninhibited or inhibited ARX10, always starting from the corrosion potential (E cor ) and reaching a cathodic polarization of -0.300 V vs E cor , in the case of the cathodic branch, and up to a current density of about 3 mA cm -2 (or + 0.5 V SCE , the first of the two limits), in the case of the anodic branch. The potential scan rate was 0.167 mV s -1 . The Levenburg-Marquardt (LEV) method was applied (by software SAI CView v.3.5c) to properly fit the coupled anodic and cathodic polarization curves to the following equation:

⎜ ⎟ = ⎛ ⎝ - ⎞ ⎠ - - j j 10 10 cor E E b E E b cor a cor c
(1) in order to evaluate the corrosion current density, j cor and the anodic and cathodic Tafel slopes (b a and b c ) [START_REF] Cao | Corrosion of ultra-high-purity Mg in 3.5% NaCl solution saturated with Mg(OH) 2[END_REF].

Surface analyses

A Scanning Electron Microscope (SEM) model ZEISS EVO MA 15, coupled to an Energy Dispersive X-Ray Spectroscopy (EDS) system (Aztec Oxford apparatus, SDD detector, WD 10 mm, EHT 20 kV), was used to characterise non-polarized samples exposed for 480 h to the aggressive solutions with and without inhibitors. Elemental EDS analyses were performed on large surface areas (1.0 × 0.5 mm 2 ) in order to determine the Cu/Sn wt% ratio before and after exposure to assess the extent of decuprification in each condition.

In addition to this elemental surface investigation, Raman and XPS spectroscopies were also performed to characterize the sample surfaces.

The Raman spectrometer used was a Renishaw InVia connected to a Renishaw SCA (Structural and Chemical Analyzer). The spectra were collected with an Ar + laser (λ = 514.5 nm) and power output less than or equal to 5 mW, to avoid surface degradation.

XPS analyses were carried out on the first atomic layers of the exposed surfaces, using a monochromatized Al-Kα source (hν = 1486.6 eV) on a ThermoScientific K-Alpha system. The X-ray spot size was about 400 μm in diameter. The photoelectron emission spectra were recorded in direct N(Ec). The pass energy was fixed at 130 eV with a step of 1 eV for surveys, and 40 eV with a step of 0.1 eV for core levels. Ionic sputtering of the surfaces was made with Ar + ion beam accelerated under 200 eV low current for 30 s, in order to remove carbon surface contamination. XPS data were fitted by using Thermo Scientific ™ Avantage Software and Shirley method was used for the background subtraction of all the peaks. Prior to testing, the samples were stored under N 2 to avoid any surface alteration.

Results

Polarization curves

The polarization curves recorded after 1 h immersion in uninhibited and inhibited solutions are reported in Fig. 2a andb. In uninhibited ARX10 (blank solution), bronze exhibited a low corrosion current density (j cor of the order of 1 μA cm -2 ) and a relatively high anodic slope up to about 0.01 V, suggesting the presence of a rather continuous and protective oxide film which is most likely to be a residual of the air-formed one. At 0.01 V, an abrupt anodic slope change occurred denoting the breakdown of the passive film, followed by fast bronze dissolution. The cathodic reaction sustaining bronze corrosion was oxygen reduction, which was under activation control at the corrosion potential, E cor , and reached a limiting reduction current after about 200 mV of cathodic polarization. This indicated that the surface film on bronze sustained a relatively slow charge transfer process controlling oxygen reduction reaction.

Fig. 2a shows that the addition of SITP, MSITP and TPIE determined a significant inhibiting effect on the cathodic reaction, shifting E cor values towards negative values. These Schiff bases also widened the passive potential range, but MSITP and TPIE did not increase the potential of film breakdown (about 0.01 V) while SITP ennobled it to 0.10 V, determining a passive potential range of about 400 mV. On the contrary, PMSI (Fig. 2b) did not significantly modify the corrosion process in comparison to that observed in the blank solution, and slightly reduced the width of the passive potential range. Finally, the addition of SIAP (Fig. 2b) stimulated the cathodic process and accelerated the corrosion of bronze due to the shift of E cor up to the potential of film breakdown. Consequently, the test in this last solution was not prolonged over 24 h.

The polarization curves recorded after 480 h immersion in the absence and in the presence of the Schiff bases except for SIAP are shown in Fig. 3a, while Table 1 reports the electrochemical parameters derived from these curves. In particular, the Table collects the E cor and j cor values, the anodic and cathodic Tafel slopes, b a and b c , and the inhibiting efficiency values (η), evaluated by the following formula:

= - × η j j j 100 cor,u cor,i cor,u (2)
where j cor,u and j cor,i refer to the corrosion current density evaluated in uninhibited and inhibited solutions, respectively, by applying the Levenburg-Marquardt (LEV) method and Eq. (1). As an example, in the case of ARX10 in the absence and in the presence of SITP Fig. 3b shows the comparison between the experimental and calculated polarization curves obtained by fitting. Some limited discrepancies were detected due to noise introduced by ohmic drop compensation, especially around E cor . However, the overall agreement achieved may be considered quite acceptable considering the scope of this research.

Fig. 3a shows that in the absence of additives, the anodic and cathodic currents were higher than those recorded at short immersion times (Fig. 2). The cathodic reaction of oxygen reduction was under mass transport control at E cor as indicated by the very high |b c | value (Table 1) and reached a limit current density of about 10 μA cm -2 , after about 100 mV of cathodic polarization. The shape of the anodic curve suggests that bronze was covered by a surface layer of corrosion products (patina), which partially protected the alloy up to about 0.170 V, where a slope change suggested a faster dissolution process. Average j cor values of about 8.3 μA cm -2 could be obtained by application of the non linear fitting method (Table 1).

After 480 h the different Schiff bases showed variable inhibiting effects towards bronze corrosion, as indicated by the range of j cor and η values reported in Table 1. In general, in spite of their low concentrations three of them (SITP, TPIE and MSITP) exhibited significant η values of 99.91, 94.6 and 77.3%, respectively. The most efficient substance, SITP, clearly behaved as a mixed corrosion inhibitor because it afforded a strong inhibition of both the cathodic and the anodic process, with passive conditions maintained up to a breakdown potential of about + 0.23 V, that is about 60 mV higher than that recorded in uninhibited solution. TPIE and MSITP could also hinder both the cathodic process, particularly in the case of TPIE, but also the anodic reaction, with the formation of rather protective surface patinas. In both cases, the anodic curves showed a film breakdown potential close to that recorded in SITP solution. Finally, PMSI negligibly inhibited the reaction of oxygen reduction and the anodic polarization curve exhibited a slope of 64.1 mV decade -1 , much lower than that recorded in the blank solution.

Since phosphonates and N-containing inhibiting mixtures showed synergistic inhibition of steel corrosion in chloride solution [START_REF] Ochoa | The synergistic effect between phosphonocarboxylic acid salts and fatty amines for the corrosion protection of a carbon steel[END_REF], an attempt was made to assess whether a mixture of saturated SITP and 10 -2 M P would also afford a similar synergistic effect for bronze. For this reason, bronze samples were exposed for 480 h to ARX10 in the presence of either the SITP + P mixture or only P salt. Final polarization curves are collected in Fig. 4, while the electrochemical parameters derived from these polarization curves are collected in Table 1. They show that P alone negligibly inhibited the cathodic reaction in the vicinity of E cor , but under anodic polarization the alloy reached a passivation potential at about + 0.07 V, above which a quite steep anodic slope was obtained with currents slowly increasing from 15 to 100 μA cm -2 without the onset of pitting attack up to + 0.5 V. The SITP + P mixture was very effective, but did not afford any synergistic inhibition because j cor was slightly higher than that obtained with SITP alone (Table 1). However, the mixture induced a stable passive condition on bronze which remained unaltered up to potentials nobler than +0.5 V.

EIS tests

A nondestructive EIS technique was used to investigate the time evolution of the corrosion process on bronze and to characterize the bronze / aggressive solution interface in ARX10, in the absence and in the presence of the various Schiff bases. In the case of SITP, the influence of P addition was also studied.

As shown in Fig. 5a andb, the dielectric behavior of bronze exposed to uninhibited ARX10 for periods longer than 1 h was characterized by three time constants, in accordance with results obtained by other authors in similar environments [START_REF] Marušić | Inhibiting effect of 4-methyl-1-ptolylimidazole to the corrosion of bronze patinated in sulphate medium[END_REF][START_REF] Marušić | Comparative studies of chemical and electrochemical preparation of artificial bronze patinas and their protection by corrosion inhibitor[END_REF][START_REF] Bostan | Evaluation of some phenothiazine derivatives as corrosion inhibitors for bronze in weakly acidic solution[END_REF]. In fact, three loops were detected in the Nyquist plots, in the frequency ranges: 10 -10 3 Hz (highfrequency (HF) loop), 10 -1 -10 Hz (medium-frequency (MF) loop), and at frequencies lower than 10 -1 Hz (low-frequency (LF) arc).

The spectra were correctly fitted by the equivalent circuit (EC) reported in Fig. 6a, where three nested R-CPE (Resistance-Constant Phase Element) couples were present. As the loops in the spectra were depressed semicircles, CPE elements were used instead of capacitances to compensate for surface roughness, porosities and other surface inhomogeneities. The impedance expression of CPE was Z = [Y(jw) n ] -1 , where w = 2πf is the angular frequency, j = √(-1) is the imaginary unit, Y is a frequency independent value and n is a fit parameter with values 0 ≤ n ≤ 1, which measure the element deviation from the ideal capacitive behaviour (exhibiting n = 1) [START_REF] Macdonald | Impedance Spectroscopy[END_REF][START_REF] Jorcin | CPE analysis by local electrochemical impedance spectroscopy[END_REF][START_REF] Hsu | Concerning the conversion of the constant phase element parameter Y0 into a capacitance[END_REF]. For each R-CPE couple, the general equation C = (R 1-n Y) 1/n was used to convert the Y parameters of the CPE elements into the associated capacitances (with R being the corresponding couple resistance) [START_REF] Bostan | Evaluation of some phenothiazine derivatives as corrosion inhibitors for bronze in weakly acidic solution[END_REF][START_REF] Brug | The analysis of electrode impedances complicated by the presence of a constant phase element[END_REF].

Previous studies allow a physical interpretation of the elements in Fig. 6a [START_REF] Marušić | Inhibiting effect of 4-methyl-1-ptolylimidazole to the corrosion of bronze patinated in sulphate medium[END_REF][START_REF] Marušić | Comparative studies of chemical and electrochemical preparation of artificial bronze patinas and their protection by corrosion inhibitor[END_REF][START_REF] Bostan | Evaluation of some phenothiazine derivatives as corrosion inhibitors for bronze in weakly acidic solution[END_REF][START_REF] Dermaj | Electrochemical and spectroscopic evidences of corrosion inhibition of bronze by a triazole derivative[END_REF][START_REF] Varvara | Evaluation of some non-toxic thiadiazole derivatives as bronze corrosion inhibitors in aqueous solution[END_REF]. In particular:

-R s is the solution resistance between the bronze electrode and the reference electrode; the R f -CPE f couple describes the dielectric properties of a surface corrosion product film (HF time constant), with R f and C f corresponding to the resistance and pseudocapacitance values of the surface film; the R t -CPE dl couple is correlated to the charge transfer reaction occurring on bronze (MF time constant) and R t and C dl are the charge transfer resistance and the capacitance of the double layer at the metal-electrolyte interface; the R F -CPE F pair (LF time constant) refers to the faradaic reactions of oxidationreduction involving the surface corrosion products (likely related to the redox reaction between Cu and Cu(I) ions, the latter incorporated into the surface film based on cuprite, Cu 2 O, in the blank solution); therefore R F and C F are the resistance of the faradaic reactions and the related pseudocapacitance value, respectively.

The n exponent values in CPE analytical expressions used to fit the depressed features of experimental Nyquist plots fall within the range 0.54-1, in analogy to previous results achieved on bronze in uninhibited and inhibited synthetic acid rain [START_REF] Marušić | Inhibiting effect of 4-methyl-1-ptolylimidazole to the corrosion of bronze patinated in sulphate medium[END_REF][START_REF] Marušić | Comparative studies of chemical and electrochemical preparation of artificial bronze patinas and their protection by corrosion inhibitor[END_REF][START_REF] Wang | The inhibition effect and mechanism of L -cysteine on the corrosion of bronze covered with a CuCl patina[END_REF].

The evolution of the bronze corrosion behavior in uninhibited ARX10 can be interpreted by discussing the EIS fitting results, also in the light of the trends shown by the polarization curves (Figs. 2 and3).

First af all, Fig. 5a shows a time evolution of the solution resistance values (R s , corresponding to the high frequency intercept of the spectra with the real axis). In fact, from 1 to 48 h of immersion, R s passed from 500 to about 800 Ω cm 2 , due to a concomitant solution pH increase from 3.3 to about 5.3, induced by the oxygen reduction reaction sustaining corrosion. At even longer immersion times (Fig. 5b), R s values remained more or less constant because of the buffering effect of dissolved copper cations determining a pH stabilization.

After 1 h immersion in ARX10, only the MF and LF time constants were distinguished in the EIS spectrum (Fig. 5a, inset), suggesting that the surface film had a negligible effect on the electrode impedance. The R f -CPE f couple was, therefore, omitted and the EC adopted is that reported in Fig. 6b. The results of the best fitting procedure are also included in Fig. 5. Quite similar results have been obtained by other authors in comparable environments [START_REF] Marušić | Inhibiting effect of 4-methyl-1-ptolylimidazole to the corrosion of bronze patinated in sulphate medium[END_REF][START_REF] Varvara | Evaluation of some non-toxic thiadiazole derivatives as bronze corrosion inhibitors in aqueous solution[END_REF]. The fitting parameters are reported in Fig. 7, together with the R p values calculated as the sum: R p = R f + R t + R F [START_REF] Bostan | Evaluation of some phenothiazine derivatives as corrosion inhibitors for bronze in weakly acidic solution[END_REF][START_REF] Varvara | Evaluation of some non-toxic thiadiazole derivatives as bronze corrosion inhibitors in aqueous solution[END_REF][START_REF] Wang | The inhibition effect and mechanism of L -cysteine on the corrosion of bronze covered with a CuCl patina[END_REF][START_REF] Rahmouni | Protection of ancient and historic bronzes by triazole derivatives[END_REF][START_REF] Varvara | Propolis as a green corrosion inhibitor for bronze in weakly acidic solution[END_REF]. Although at 1 h immersion a clear time constant related to the surface film was not detected, bronze exhibited a passive behaviour as evidenced by the high anodic slope in the 1 h anodic polarization curve (Fig. 2). The surface film, likely residual of the air-formed oxide film, determined a relatively high charge transfer resistance (a high R t at 1 h immersion), thus justifying the low cathodic currents in the blank polarization curves of Fig. 2 [START_REF] Chiavari | Atmospheric corrosion of fire-gilded bronze: corrosion and corrosion protection during accelerated ageing tests[END_REF]. At increasing immersion times, the film underwent a fast alteration in contact with the aggressive solution because after 2 h immersion R t and R p had already shown a significant decrease.

Until about 260 h, rather low and constant R f and R t values were achieved. They then tended to increase slightly with time as a consequence of the accumulation of corrosion products hindering the alloy oxidation. This was in agreement with the shape of the anodic polarization curve recorded on bronze after 480 h of immersion (Fig. 3), which exhibited a relatively high anodic slope of 90.2 mV/decade. The decrease in C f pseudocapacitance values after 360 h confirmed the increase in film thickness at long immersion times, while the C dl diminution, particularly in the second half of the immersion, was most likely a consequence of the decrease in the surface area of the active anodic regions under the surface film.

R F , connected to the resistance of the faradaic reaction of interchange between Cu and Cu(I), significantly decreased during most of the immersion period because the Cu 2 O film, which is expected to have a high faradaic activity, grew on the surface and caused an increase in region areas where the reaction may occur. A final increase in R F trend may have been connected to the final decrease in film porosity with a consequent decrease in the electrolyte accessibility to the metal/Cu 2 O interface. This variation of the metal/Cu 2 O interface area also affected C F which accordingly showed an opposite trend to R F , in particular an initial fast, followed by a slow increase and a final decrease.

In SITP solution, due to the strong inhibition of the corrosion process, a limited pH variation was detected during bronze immersion (final pH values = 3.5) and consequently rather constant R s values (in the range 450-550 ohm cm 2 ) were measured. With this very efficient inhibitor only the HF and MF loops were detected, while the LF loop connected to the faradaic reactions was absent at all immersion times. This suggests that the inhibitor adsorption produces a highly stable surface film with low Cu(I) ⇆ Cu reactivity. The evolution of the SITP spectra is shown in Fig. 8a, which clearly evidences an increase in bronze corrosion resistance during time. The two time constant-EC reported in Fig. 6c was used for curve fitting and the parameters achieved by data interpolation are reported in Fig. 7, where they can be compared to those in the blank solution. The high and increasing corrosion resistance of bronze was connected to a high R t which rose up to about 5 MΩ cm 2 and to R f , which increased with time by more than two orders of magnitude and finally reached a value over 1 MΩ cm 2 . This suggests that SITP appears to produce a protective surface film which hinders charge transfer from the very beginning of the immersion. The concomitant limited decrease in C f pseudocapacitance values suggests that the thickness of the SITP film grows only slightly with time and its increasing resistance is likely connected to a progressively more compact and resistive nature. C dl decreased by one order of magnitude with time, which may reasonably be put down to a decrease in surface area on which charge transfer may occur while the film density increases and/or to a progressive substitution of water molecules (with high dielectric constant) by adsorbed organic inhibitor molecules (with low dielectric constant) within the double layer.

Given its interesting anodic behavior, the inhibition mechanism of the mixture SITP + P was also investigated by means of EIS spectra fitting. In this case, during bronze immersion no pH variation and rather constant R s values were detected. These latter values were lower than those measured in SITP solution (about 200 Ω cm 2 ), due to the presence of 10 -2 M P (sodium dihydrogen phosphate salt). Selected spectra among those recorded during the 480 h immersion period are presented in Fig. 8b. They are quite different from those recorded in the presence of SITP alone, as they are again best fitted by the three time constant-EC of Fig. 6a. Therefore, although in this solution bronze underwent a much slower corrosion process than in the blank, the electrode impedance was affected by the same contributions found in the blank solution: the dielectric properties of a surface film, a charge transfer process at the electrode surface and a faradaic reaction involving the surface film. The fitting parameters can be compared to those obtained in the presence of SITP alone and in the blank solution in Fig. 7.

Within 72 h of immersion, R f was higher than in SITP solution (values around 40-50 kΩ cm 2 ) and then set at about 30 kΩ cm 2 . These final values were more than one order of magnitude lower than the final ones achieved in SITP solution, while only slightly lower R t values were obtained, setting at about 1 MΩ cm 2 . R F was always higher than R t and followed the same R t trend. The presence of the R F -C F couple in the EC suggests that in SITP + P solution the film exhibits a faradaic activity, but is less susceptible to redox processes than in the blank solution, as indicated by much higher R F and much lower C F values. Within the initial 2-3 days of exposure, C f and C dl decreased slowly and then remained more or less constant, suggesting a limited increase in the film thickness and a contemporary decrease in the metal surface area available for charge transfer. All these findings indicate that the addition of P to SITP solution changed the characteristics of the surface film. In particular, even at short immersion times P contributed to producing a resistive film which did not then evolve significantly. Although this film maintained a low faradaic activity it was higher than that of the SITP film. In general, these variations induced high R p values (Fig. 7d), even higher than those presented by SITP alone within 3 days of immersion, but, in accordance with polarization curve results, they were comparable to those obtained by SITP during long immersion times.

With the exception of SITP, the other Schiff bases showed EIS spectra with three time constants, like those in the blank solution, and could be fitted with the EC in Fig. 6a. As an example, Fig. 9 shows the agreement between the experimental spectra obtained in the presence of the Schiff bases at the end of the immersion period and those obtained by the fitting procedures (χ 2 values ≤ 0.0007).

The R p (calculated as the sum of R f , R t and R F ) and the corresponding E cor values obtained on bronze with time in the absence and presence of all Schiff bases are reported in Fig. 10.

In comparison to the blank, SIAP addition did not modify bronze corrosion behavior in ARX10 (as also indicated by the spectrum in the inset of Fig. 9); this was likely due to its low concentration and scarce adsorption capability. Instead, TPIE and MSITP, but also PMSI to a limited extent, presented an inhibition effect, in agreement with the results of the polarization curves. The concurrent E cor evolution exhibited quite negative initial values, often more active than those in the blank, suggesting that they initially acted as cathodic inhibitors. Their surface films then became more protective and their E cor values reached and exceeded those in the blank solution. In conclusion, as also indicated by the recorded polarization curves, SITP, TPIE and MSITP act as mixed corrosion inhibitors.

The inhibiting efficiencies of the Schiff bases and SITP + P formulation after 480 h immersion calculated from R p values (R p,i in inhibited and R p,u in uninhibited blank solutions) by the formula:

= - × η R R R 100 R p,i p,u p,i p (3)
are given in Table 1. They are in overall good agreement with those achieved from polarization curve analysis and confirm them. In the case of SIAP (inset), the spectrum was recorded after 24 h of immersion.

SEM-EDS analysis

Fig. 11 collects SEM observations obtained on unexposed bronze samples and on samples after 1 h or 480 h of immersion in ARX10 solution, both in the absence of inhibitors and in the presence of SITP or SITP + P. Fig. 11a, related to unexposed bronze, clearly shows that the alloy was an α-cored bronze with dendritic microstructure, with Sn-an Sb-local enrichment also revealing the Pb globules (white spots in the BSE image of Fig. 11a) in the interdendritic regions.

In ARX10 the corrosion of uninhibited bronze (Fig. 11b andc) was significant and mainly localized in the core of dendritic regions and at Pb globules. The latter attack is more visible at short immersion times (Fig. 11b), where many small black holes were visible in the interdendritic region, due to the dissolution of the white Pb globules clearly evident on unexposed bronze (Fig. 11a). This behavior is in agreement with the lower nobility of Pb in comparison to Cu, as assessed during tests on pure metals in ARX10 [START_REF] Chiavari | Protective silane treatment for patinated bronze exposed to simulated natural environments[END_REF]. The corrosion attack was quite limited in SITP solution (Fig. 11d ande). In this case, only partial Pb globule dissolution occurred at long immersion times leaving a few small holes in the corresponding areas. In the presence of the SITP + P inhibiting mixture (Fig. 11f andg), the corrosion attack was also very light and, at the end of the immersion, was localized on Pb while the visible dendritic aspect vanished.

Overall, the SEM-EDS analysis after 480 h of immersion revealed the presence of chlorides at a concentration of 0.3 ± 0.1 wt.% on the surface of the sample exposed to non-inhibited solution, while in the presence of SITP and SITP + P these aggressive anions were not detectable. Moreover, in the absence of inhibitors, the phenomenon of decuprification took place on the bronze surface with a reduction in the Cu / Sn wt.% ratio from 34.3 (before exposure) to 15.1 (after 480 h of exposure to ARX10). Instead, after 480 h in the presence of inhibitors, this ratio remains equal to 34.3 in the presence of SITP, and was slightly reduced to 29.4 in the presence of SITP + P. This confirms the lower dissolution of copper from the alloy in the presence of SITP or SITP + P compared to the blank solution.

Raman spectroscopy

Raman spectroscopy performed on bronze exposed for 480 h in ARX10 confirmed the presence of typical products found in outdoor bronze patinas. Large crystals of Cu 2 O and few isolated crystals of posnjakite (Cu 4 (SO 4 )(OH) 6 •(H 2 O)) were found in the core of dendrites, while Cu 2 O and traces of nanocrystalline SnO x •(H 2 O) y were detected in the interdendritic regions.

Raman spectra on SITP-protected bronze showed very pronounced fluorescence bands, suggesting the presence of a surface film containing the organic inhibitor. Also in the case of SITP + P, the Raman spectra were poorly readable, due to the presence of intense fluorescence bands.

XPS spectroscopy

In order to obtain information on the inhibition mechanism occurring on bronze, the XPS technique was applied on unexposed samples and on samples exposed for 480 h to ARX10, both in the absence and in the presence of SITP or SITP + P.

As regards the unexposed bronze, the surface XPS analysis (survey in Fig. 12a) detected the presence of Cu, Pb and Sn among the alloying elements, and C and O as environmental contaminants. The presence of Zn or Sb was not highlighted. By analyzing the areas of the deconvoluted profiles in the high-resolution spectra (core levels, in Fig. 13), it was possible to quantify each peak component in atomic percentages, as summarized in Table 2, together with the corresponding binding energies (BE) [START_REF] Masi | X-ray Photoelectron Spectroscopy as a tool to investigate silane-based coatings for the protection of outdoor bronze: The role of alloying elements[END_REF]. Cu and Sn were detected on the surface both in the metallic and oxidized state (Table 2) while Pb was mainly present as an oxide, suggesting that surface polishing and air oxidation produces a thin film of corrosion products. Cu 2p core level and Auger spectra (Cu LMM) are reported in Fig. 13e andf, respectively. The former spectrum showed a high peak at 932.5 eV and no shake-up satellite peak at 940-944 eV, suggesting the possible presence of Cu(I) and/or Cu(0) [START_REF] Qafsaoui | Coupling of electrochemical, electrogravimetric and surface analysis techniques to study dithiocarbamate/bronze interactions in chloride media[END_REF][START_REF] Mezzi | Investigation of the benzotriazole inhibition mechanism of bronze disease[END_REF]. The Auger Cu L 3 M 4,5 M 4,5 signals at 916.8 eV and 918.7 eV (Kinetic Energy, KE) well corresponded to a mix of Cu(I) and Cu(0) species, respectively [START_REF] Qafsaoui | Coupling of electrochemical, electrogravimetric and surface analysis techniques to study dithiocarbamate/bronze interactions in chloride media[END_REF][START_REF] Sinapi | Monolayers and mixed-layers on copper towards corrosion protection[END_REF]. Fig. 13g shows quite small Sn3d signals (Sn3d 5/2 at 486 eV and Sn3d 3/2 at 494 eV). The deconvolution of Sn 3d 5/2 (Fig. 13g) suggested the concomitant presence of Sn(0) at 4847 eV and Sn(II) at 4858 eV, both in negligible amounts (Table 2) [START_REF] Kövér | Electronic structure of tin oxides: high-resolution study of XPS and Auger spectra[END_REF][START_REF] Robbiola | Characterisation of anodic layers on Cu-10Sn bronze (RDE) in aerated NaCl solution[END_REF][START_REF] Sinsermsuksakul | Overcoming efficiency limitations of SnS-based solar cells[END_REF][START_REF] Rodriguez | Surface chemistry of SO2 on Sn and Sn/Pt(111) alloys: effects of metal-metal bonding on reactivity toward sulfur[END_REF][START_REF] Hutchison | Enhanced electrochemical Cu release from commercial Cu-Sn alloys: fate of the alloying elements in artificial perspiration[END_REF]. Instead, the core level spectrum of Pb 4f (Fig. 13h) showed a peak at 138.1 eV (Pb4f 7/2 ) to be ascribed to oxidized Pb and revealed that no metallic Pb was present on the surface [START_REF] Chan | Characterization of the patina formed on a low tin bronze exposed to aqueous hydrogen sulfide[END_REF][START_REF] Masi | Corrosion investigation of fire-gilded bronze involving high surface resolution spectroscopic imaging[END_REF]. This film constituted of limited Cu(I), Sn(II) and Pb oxide species was most likely still present on bronze after 1 h immersion in ARX10 and was responsible for the significant bronze corrosion resistance shown by the A quite different film was present after long immersion periods in the blank solution (survey spectrum in Fig. 12b). In fact, beside surface C contamination (core level spectrum in Fig. 13a), this film was characterized by the presence of a small N 1 s peak at 399.6 eV, compatible with the deposition of small amounts of ammonium compounds after reaction with ammonium ions in ARX10 (Fig. 13b), and a high O1 s peak at 531.0 eV (Fig. 13c), compatible with oxide formation [START_REF] Masi | X-ray Photoelectron Spectroscopy as a tool to investigate silane-based coatings for the protection of outdoor bronze: The role of alloying elements[END_REF]. Cu 2p core level spectrum (Figs. 13e) showed a high peak at 932.3 eV and a smaller one at 934.5 eV, with a significant shake-up satellite peak at 940-944 eV, suggesting the concomitant presence of Cu(I)/Cu(0) and Cu (II) species. The Auger Cu L 3 M 4,5 M 4,5 signal at 916.8 eV (kinetic energy, KE) and the shoulder at lower KE suggested the presence of Cu (I) and Cu(II) compounds [START_REF] Finšgar | EQCM and XPS analysis of 1,2,4-triazole and 3-amino-1,2,4-triazole as copper corrosion inhibitors in chloride solution[END_REF]. Core level spectra of Sn 3d (Fig. 13g), Pb 4f (Fig. 13h) and Sb 3d (the last one not reported in Fig. 13) showed peaks at 486.7 eV (Sn3d 5/2 ), 138.5 eV (Pb4f 7/2 ) and 540.1 eV (Sb3d 3/2 ), respectively, indicating the presence of Sn(IV) [START_REF] Kövér | Electronic structure of tin oxides: high-resolution study of XPS and Auger spectra[END_REF][START_REF] Robbiola | Characterisation of anodic layers on Cu-10Sn bronze (RDE) in aerated NaCl solution[END_REF][START_REF] Sinsermsuksakul | Overcoming efficiency limitations of SnS-based solar cells[END_REF][START_REF] Rodriguez | Surface chemistry of SO2 on Sn and Sn/Pt(111) alloys: effects of metal-metal bonding on reactivity toward sulfur[END_REF][START_REF] Hutchison | Enhanced electrochemical Cu release from commercial Cu-Sn alloys: fate of the alloying elements in artificial perspiration[END_REF], Sb(III) [START_REF] Yang | pH-regulated template-free assembly of Sb 4 O 5 Cl 2 hollow microsphere crystallites with self-narrowed bandgap and optimized photocatalytic performance[END_REF] and Pb) [START_REF] Chan | Characterization of the patina formed on a low tin bronze exposed to aqueous hydrogen sulfide[END_REF][START_REF] Masi | Corrosion investigation of fire-gilded bronze involving high surface resolution spectroscopic imaging[END_REF] oxides. As regards Pb, the binding energies of Pb oxides were too close to each other to allow for a precise attribution, but, on the basis of the E cor values of bronze in ARX10, the presence of Pb(II) (PbO-like) species was more likely [START_REF] Paparazzo | Surface and interface microchemistry of archaeological objects studied with X-ray Photoemission Spectroscopy and scanning Auger microscopy[END_REF].

The XPS results reported in Table 2 confirm the surface decuprification of bronze due to corrosion revealed from the SEM-EDS analysis. The Cu/Sn atomic ratio decreased from about 29 in the unexposed sample to 1.16 after exposure to the blank solution. Also Pb underwent a preferential dissolution because of a concurrent significant decrease in Pb/Sn ratio.

After 480 h of immersion in SITP solution (survey in Fig. 12b), XPS spectra revealed the formation of a SITP-containing film, as indicated by the increase in the content of the inhibitor elements. In fact, an increase in the N 1 s peak at 399.2 eV, related to organic NeC bonds [START_REF] Tommesani | On the protective action of 1,2,3-benzotriazole derivative films against copper corrosion[END_REF][START_REF] Kosec | Impedance and XPS study of benzotriazole films formed on copper, copper-zinc alloys and zinc in chloride solution[END_REF][START_REF] Qafsaoui | Coupling of electrochemical, electrogravimetric and surface analysis techniques to study dithiocarbamate/bronze interactions in chloride media[END_REF] (Fig. 13b), and a rise in specific C 1 s and S 2p signals were detected. In particular (Fig. 13a), instead of the C1 s peak at 287.5 eV related to surface contaminants which almost disappeared, high C 1 s peaks at 284.4 eV and 286.0 eV were obtained: the former corresponding to organic CeC and CeH bonds, and the latter related to CeO, CeS and CeN bonds [START_REF] Sinapi | Monolayers and mixed-layers on copper towards corrosion protection[END_REF]. The intense S 2p 3/2 peak at 163.5 eV was also related to SeC and SeH bonds of the inhibitor, while the shoulder at 162.3 eV suggested the interesting formation of coordination bonds of S-Cu type [START_REF] Qafsaoui | Coupling of electrochemical, electrogravimetric and surface analysis techniques to study dithiocarbamate/bronze interactions in chloride media[END_REF][START_REF] Sinapi | Monolayers and mixed-layers on copper towards corrosion protection[END_REF]. The third shift of S 2p transition was indicative of the deposit of quite limited amounts of sulphates as corrosion products (Fig. 13d) [START_REF] Finšgar | 2-mercaptobenzimidazole as a copper corrosion inhibitor: part II. Surface analysis using X-ray photoelectron spectroscopy[END_REF]. Analysis of the Cu 2p core level (Fig. 13e) disclosed a small peak (much smaller than in the blank) at 932.7 eV and a shoulder at 934.5 eV, with a tiny shake-up satellite peak at 940-944 eV. This spectrum, in association with the Auger Cu L 3 M 4,5 M 4,5 signal at 916.0 eV (KE) (Fig. 13f), was indicative of the predominant presence of Cu(I) species over Cu (II) species (Table 2) [START_REF] Finšgar | EQCM and XPS analysis of 1,2,4-triazole and 3-amino-1,2,4-triazole as copper corrosion inhibitors in chloride solution[END_REF], meaning, therefore, that the surface film was essentially composed of Cu(I)-SITP complexes based on Cu(I)-S bond formation. The intense S 2p 3/2 at 163.5 eV, correlated to SeH and/or SeC, was even more pronounced than that related to the S-Cu(I) structure, suggesting the concomitant presence of adsorbed SITP molecules in the film not involved in complex formation. This would also justify the high N / Cu(I) ratio (much higher than 1) again correlated to the presence of adsorbed SITP molecules, in addition to Cu(I)-SITP complexes. The XPS analysis also detected small amounts of sulphates, most likely Cu(II) salts.

In the presence of SITP + P, quite similar results were achieved, confirming the formation of a SITP film of adsorbed molecules and Cu (I)-complexes. However, in this case the atomic percentages of N atoms and S atoms related to the inhibitor (i.e. both S-Metal and SeH/S-C bonds) and particularly the Cu(I) species (likely involved in the complex formation) were lower than in the sample exposed to SITP. This would suggest that both the overall SITP amount and particularly the relative quantity of Cu(I)-SITP complexes per adsorbed molecules were smaller than in the case of the SITP alone. Thus, a thinner SITP film is to be expected with a smaller Cu complex fraction. Again, in comparison to SITP sample, the SITP + P sample also showed slightly higher amounts of Cu(II) ions and S atoms involved in sulphate species. Finally, a limited but significant atomic percentage of phosphorus atoms ascribed to phosphates [START_REF] Li | Synergetic tuning charge dynamics and potentials of Ag 3 PO 4 photocatalysts with boosting activity and stability by facile insitu fluorination[END_REF] in the film was detected, most likely connected to the surface precipitation of Cu(II) phosphates at film defects where the concentration of dissolved Cu(II) ion was higher. This mechanism of defect healing may have been present in the film since the beginning of the immersion.

In agreement with SEM observation, no Pb signal was detected, in either SITP or SITP + P solutions, due to its significant dissolution after long immersion times, as previously evidenced by SEM observation (Fig. 11).

Discussion

The investigated Schiff bases afford quite different inhibiting efficiency (η) values, as a result of their different concentrations and molecular structures. In spite of their limited solubility determining low saturation concentrations, high η values of 77.3, 94.6 and 99.91% are obtained by addition of MSITP, TPIE and SITP, respectively, in good agreement with η Rp values, meaning that small amounts of these substances are sufficient to protect bronze. These substances contain a mercapto group in the molecule, which ensures a stronger chemisorption on bronze, due to its high chemical affinity with Cu cations on bronze surface. In the case of SITP, exhibiting the highest solubility, the best inhibition performances were accordingly achieved. Polarization curves recorded after 480 h immersion in ARX10 show that these three substances act as mixed corrosion inhibitors and increase the potential of surface film breakdown by chlorides on bronze.

By addition of P to SITP solution, excellent η quite close to that in SITP solution and a remarkable increase in breakage potential is achieved. Therefore, the inhibition mechanisms of both SITP and SITP + P additives were investigated by a combination of electrochemical and surface analysis techniques.

Surface analyses show that these substances induce a strong modification of the surface film, which in the blank solution is largely composed of Cu 2 O, hydrated SnO x , PbO-like oxide. According to XPS results, the surface film formed in SITP solution contains both Cu(I)-SITP complexes, based on Cu(I)-S bond formation, and adsorbed SITP molecules. Quite similar results have been obtained by other authors [START_REF] Castro | Growth of 2-mercaptobenzoxazole on Cu(100) surface: chemisorbed and physisorbed phases[END_REF] with different S-containing organic inhibitors of copper corrosion, which were reported to produce duplex organic films, including a first chemisorbed layer, on top of which a physisorbed multilayer grows. The stability of the multilayer arises because of π-stack interactions between aromatic rings and Van der Waals bonds between polarizable substitutional functional groups [START_REF] Antonijević | Copper corrosion inhibitors. A review[END_REF][START_REF] Rao | Formation, characterization and corrosion protection efficiency of self-assembled 1-octadecyl-1H-imidazole films on copper for corrosion protection[END_REF]. EIS analysis clearly highlights that in SITP solution the film builds up with time and is quite stable, with negligible Cu(I) ⇆ Cu reactivity. Despite the slow growth, it is able to hinder charge transfer and offers high protectiveness already at short immersion times.

The addition of P to SITP solution determines the formation of a thinner surface film (as suggested by XPS results and by the relatively small R f values obtained by EIS), again composed of a first Cu(I)-SITP complex layer, covered by adsorbed SITP molecules. In comparison to the film in SITP solution, the presence of a smaller fraction of Cu(I)-SITP complex could negatively affect the adhesion of the film on bronze, thus justifying its higher faradaic activity. However, the precipitation of Cu(II) phosphate at flaws of the inhibitor film helps to limit the solution access to the metal surface, so maintaining high R t and finally high overall R p values. Pore plugging by Cu(II) phosphate precipitation is stimulated during anodic polarization, leading to strong passive conditions.

Conclusions

1 Among the new Schiff bases specifically synthesized and tested as bronze corrosion inhibitors in tenfold concentrated synthetic acid rain (ARX10), those containing a mercapto group exhibit good inhibiting efficiencies during 480 h immersions. In particular, SITP characterized by the highest solubility (about 0.7 mM, in comparison to 0.4 mM of TPIE and 0.3 mM of MSITP) shows an inhibiting efficiency value of almost 100%. 2 SITP protects bronze by forming a surface film containing both Cu (I)-SITP complexes and SITP molecules, the latter most likely physisorbed on the first Cu(I)-SITP layer. 3 In the presence of SITP and sodium dihydrogen phosphate (P), bronze results more resistant against localized attack. 4 In SITP + P solution, a SITP thinner film forms on bronze. P determines the precipitation of Cu(II) phosphates at flaws of the surface film, particularly under anodic polarization. 5 SITP and SITP + P addition significantly hinders bronze decuprification.

Fig. 1 .

 1 Fig. 1. Structural formulas of the Schiff bases studied as bronze corrosion inhibitors.

Fig. 2 .

 2 Fig. 2. Polarization curves recorded on bronze after 1 h of immersion in ARX10 solution: a) in the absence (1) and in the presence of SITP (2), MSITP (3) and TPIE (4); b) in the absence (1) and in the presence of PMSI (5) and SIAP (6).

Fig. 3 .

 3 Fig. 3. Polarization curves recorded on bronze after 480 h of immersion in ARX10 solution: a) in the absence (1) and in the presence of SITP (2), MSITP (3), TPIE (4) and PMSI (5); b) comparison of experimental and calculated E/j curves to evaluate the corrosion current density, jcor.

Fig. 4 .

 4 Fig. 4. Polarization curves recorded on bronze after 480 h of immersion in ARX10 solution in the absence (1) and in the presence of SITP (2), SITP + P (3) and only P (4).

Fig. 5 .

 5 Fig. 5. Nyquist diagrams from EIS tests carried out on bronze exposed to ARX10 solution for (a) 1 to 48 h and for (b) 168 to 480 h. The complete spectra obtained after 1 h and 480 h are shown in the insets.

Fig. 6 .

 6 Fig. 6. Equivalent circuits (EC) with three (a) or two (b, c) time constants, used to fit the experimental EIS spectra.

Fig. 7 .

 7 Fig. 7. Time evolution of the calculated resistance (a-d) and capacitance (e-g) values, during immersion of bronze in ARX10 solution in the absence and in the presence of SITP and SITP + P.

Fig. 8 .

 8 Fig. 8. Nyquist diagrams from EIS tests carried out on bronze immersed for different times in ARX10 solution in the presence of SITP (a) and SITP + P (b). The insets show the complete spectra obtained after 1 h in the presence of SITP (a) and SITP + P (b).

Fig. 9 .

 9 Fig. 9. Nyquist diagrams from EIS tests carried out on bronze immersed for 480 h to ARX10 solution in the presence of the different Schiff bases. In the case of SIAP (inset), the spectrum was recorded after 24 h of immersion.

Fig. 10 .

 10 Fig. 10. Time evolution of R p (a) and E cor (b) values during immersion of bronze specimens in ARX10 solution, in the absence and in the presence of the Schiff bases.

Fig. 11 .

 11 Fig. 11. BSE-SEM micrographs obtained on bare bronze samples (a) and on samples after 1 h (b,d,f) or 480 h (c,e,g) of immersion in ARX10 solution, both in the absence of inhibitors and in the presence of SITP or SITP + P.

Fig. 12 .

 12 Fig. 12. XPS surveys spectra on the reference unexposed bronze sample (a) and on bronze specimens exposed for 480 h (b) to ARX10 solution non containing (black), or containing SITP and SITP + P.

Fig. 13 .

 13 Fig. 13. XPS core level spectra of C1 s (a), N1 s (b), O1 s (c), S2p (d), Cu Auger LMM (e), Cu2p (f), Sn3d (g) and Pb4f (h), collected on the unexposed sample and on samples exposed for 480 h to uninhibited (Blank) or inhibited (SITP o SITP + P) ARX10 solution.

Table 1

 1 Corrosion potentials (E cor ), corrosion current densities (j cor ), anodic and cathodic Tafel slopes (b a , b c ) and inhibiting efficiencies calculated from both j cor (that is η) and from polarization resistance values (η Rp ), after 480 h of immersion in ARX10 solution, in the absence and in the presence of the Schiff bases. All data are presented with their corresponding standard deviations.

		E cor /	j cor /	b a /	| b c | /	η /	η Rp /
		V SCE	μA cm -2	mV decade -1	mV decade -1	%	%
	Blank	0.055 ± 0.013	8.3 ± 1.1	90.2 ± 6.7	∞	-	-
	SITP	0.017 ± 0.015	0.0082 ± 0.0025	170 ± 16	200 ± 13	99.91 ± 0.03	99.91 ± 0.04
	MSITP	0.054 ± 0.013	1.92 ± 0.62	92.3 ± 5.4	530 ± 41	77.3 ± 6.8	83.3 ± 5.1
	TPIE	0.036 ± 0.024	0.46 ± 0.21	76.1 ± 8.2	420 ± 58	94.6 ± 2.3	96.1 ± 2.5
	PMSI	0.072 ± 0.020	5.1 ± 1.0	64.1 ± 5.8	∞	33 ± 11	36 ± 21
	SITP + P	0.078 ± 0.018	0.018 ± 0.010	290 ± 11	270 ± 14	99.83 ± 0.09	99.91 ± 0.04
	P	0.024 ± 0.012	6.0 ± 1.8	60.2 ± 7.1	180 ± 15	19 ± 18	11 ± 15

Table 2

 2 XPS elemental analysis (global composition normalized to 100%) obtained from high-resolution core level spectra of unexposed bronze samples and samples exposed for 480 h to ARX10 solution both in the absence of inhibitors and in the presence of SITP or SITP + P.

	Specimen	C 1 s			N 1 s	O 1 s	P 2p	S 2p 3/2			Cu 2p 3/2		Sn 3d 5/2		Sb 3d 3/2 Pb 4f 7/2
						#
		CC, CH C-O*,	C = O,	NC, NH			S-Metal SH, S-C,	Sulfate	(Cu°) Cu	Cu(II) Sn°Sn(II)	Sn	oxide	PbO-like
			C-S,	O-C = O					…	…	(I)			(SnO)	(IV) (SnO 2 )	(s)	(s)
			C-N
	Not
	exposed
	BE (eV)	284.4	286.0 287.3 &		531.3 -	-	-	-	932.5	934.0 484.7 485.8	-	-	138.1
				288.2
	at. %	42.5	5.2*	7.5		31.1					7.2	1.6	< 0.1 0.3	-	-	4.7
	Blank 480h
	BE (eV)	284.5	286.0 287.6 &	399.6	531.0 -	-	-	-	932.3	934.5 -	-	486.7	540.1	138.5
				288.7
	at. %	17.1	11.7	8.2	1.8	40.2					4.8	4.6			8.1	2.2	1.3
	SITP 480h
	BE (eV)	284.4	285.8 287.5	399.2	532.0		162.3	163.5	167.4	932.7	934.5 -	-	-	-	-
	at. %	48.6	14.2	4.7	7.9	11.6		3.5	5.5	0.9	2.5	0.7
	SITP + P 480h
	BE (eV)	284.5	286.1 288.0	399.5	531.5 132.9 162.3	163.7	167.7	932.6	934.6 -	-	-	-	-
	at. %	48.0	15.3	3.2	6.5	16.0	0.2	2.2	3.7	1.8	1.2	2.0

# very broad peak including oxide, hydroxide, C-O and sulfate bindings.

C.Monticelli et al.

Acknowledgments

This research was carried out in the scope of the B-IMPACT project (project ID 1149) within the M-ERA.NET 2013 network, supported by the national funding organisations: Ministrstvo za izobraževanje, znanost in šport (MIZS) Slovenia, Ministero dell'Istruzione, dell'Università e della Ricerca (MIUR) Italy and Region Midi-Pyrénéés (RMP) France.