A Lepicard

T Cardinal

E Fargin

F Adamietz

V Rodriguez

K Richardson

M Dussauze
email: marc.dussauze@u-bordeaux.fr

Micro-structuring the Surface Reactivity of a Borosilicate Glass via Thermal Poling

Keywords: thermal poling, surface reactivity, micro-patterning

Thermal poling was proven successful to induce second order nonlinear properties and concurrent modification of composition, structure and chemical reactivity in glasses. With current efforts to reduce devices sizes in components employing such attributes, means to control changes at the micrometer scale are needed. We present a micro-imprinting poling process to locally tailor surface properties of a glass. Measurements using infrared, Raman and second harmonic generation microscopies confirm that changes in glass structure associated with an induced static electric field are responsible for the enhanced surface reactivity that is successfully controlled at the micrometer scale.

New developments in integrated photonics, nanotechnology, lab-on-a-chip and other photonic applications require local control of the surface properties to develop "smart substrates". Glasses are ideal materials for such applications as they have good optical properties and are easy to manufacture. Recently, we demonstrated modification of glass surface reactivity using thermal poling. [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF] Specifically, we showed that it was possible, through careful selection of the parent glass composition, to induce a charged structure in the glass' surface, yielding an enhancement of surface affinity towards atmospheric water.

Thermal poling is performed on a sample heated below its glass transition temperature. The temperature is high enough to increase the mobility of cations present inside the glass matrix. A strong DC electric field is then applied across the sample which induces charge dissociation at the anodic side of the poled glass. Upon thermal poling various types of charges are moving; their nature and role has been the center of many discussions in the literature and a complete description of the process is yet to be found. The process implying positive charge migration has been thoroughly described and is accepted by the community. Under the electric field, positive charges migrate towards the cathode. The process taking place is mainly a cationic conduction which involves sodium cation migration for the most part. Over time, a layer depleted of these cations is formed under the anodic surface. [START_REF] Carlson | Ion Depletion of Glass at a Blocking Anode -1, 2[END_REF] For glasses containing more than one cationic specie, other cations also migrate and accumulate at the limit between the sodium depleted layer and bulk glass. [START_REF] Lepienski | Electric Field Distribution and Near-Surface Modifications in Soda-Lime Glass Submitted to a Dc Potential[END_REF][START_REF] Zakel | On the Mechanism of Field-Induced Mixed Ionic-Electronic Transport during Electro-Thermal Poling of a Bioactive Sodium-Calcium Phosphosilicate Glass[END_REF] If positive charge migration alone is taken into account, the static electric field building up at the anode quickly reaches value exceeding the dielectric breakdown. It is thus necessary to account for further compensation processes which are strongly dependent on the poling conditions, blocking versus non-blocking electrodes, and on the glass itself. If thermal poling is performed in non-blocking electrodes conditions, protons and water can be injected inside the glass through the anode. [START_REF] Carlson | Anodic Proton Injection in Glasses[END_REF][START_REF] Cremoux | Trapped Molecular and Ionic Species in Poled Borosilicate Glasses: Toward a Rationalized Description of Thermal Poling in Glasses[END_REF] When the treatment is performed under blocking anode conditions, only species present inside the glass matrix prior poling come into play during the process. Negative charges are thought to play a role in that process by migrating towards the anode. [START_REF] Dussauze | Structural Rearrangements and Second-Order Optical Response in the Space Charge Layer of Thermally Poled Sodium-Niobium Borophosphate Glasses[END_REF][START_REF] Ziemath | Compositional and Structural Changes at the Anodic Surface of Thermally Poled Soda-Lime Float Glass[END_REF] The nature and conduction mechanisms of these negative charge carriers are still unclear but several hypotheses have been suggested. Carlson first suggested that oxygen anions were forming and then migrate towards the anode where they would be neutralized. [START_REF] Carlson | Polarization" in Alkali-Containing Glasses[END_REF] This argument for the presence of an oxygen depleted layer has been proven true in several papers. [START_REF] Schmidt | In Situ Investigation of Ion Drift Processes in Glass during Anodic Bonding[END_REF][START_REF] Nitzsche | Ion Drift Processes in Pyrex-Type Alkali-Borosilicate Glass during Anodic Bonding[END_REF] Other studies have mentioned that molecular oxygen could be forming through oxidation of oxygen anions and that conduction was then taking place through the electrons release during oxidation. [START_REF] Dussauze | Structural Rearrangements and Second-Order Optical Response in the Space Charge Layer of Thermally Poled Sodium-Niobium Borophosphate Glasses[END_REF][START_REF] Dussauze | Polarization Mechanisms and Structural Rearrangements in Thermally Poled Sodium-Alumino Phosphate Glasses[END_REF][START_REF] Dussauze | Thermal Poling of Optical Glasses: Mechanisms and Second-Order Optical Properties[END_REF] However, other studies have suggested that the process also present a strong electronic contribution. [START_REF] Krieger | Field Assisted Transport of Na+ Ions, Ca2+ Ions and Electrons in Commercial Soda-Lime Glass I: Experimental[END_REF][START_REF] Lipovskii | Bleaching Versus Poling: Comparison of Electric Field Induced Phenomena in Glasses and Glass-Metal Nanocomposites[END_REF][START_REF] Mariappan | Mechanism and Kinetics of Na+ Ion Depletion Under the Anode during Electro-Thermal Poling of a Bioactive Glass[END_REF] When the internal electric field reaches value close to the dielectric breakdown, the electronic charge carriers come into play and are no longer negligible, [START_REF] Zakel | On the Mechanism of Field-Induced Mixed Ionic-Electronic Transport during Electro-Thermal Poling of a Bioactive Sodium-Calcium Phosphosilicate Glass[END_REF][START_REF] Mariappan | Mechanism and Kinetics of Na+ Ion Depletion Under the Anode during Electro-Thermal Poling of a Bioactive Glass[END_REF][START_REF] Keller | Breakdown and Electric Conductivity of Glass[END_REF] formation of oxygen can then be accounted for through bond breakage and formation of peroxide radicals. Two of these peroxide entities would then react to form molecular oxygen. [START_REF] Redkov | How does Thermal Poling Produce Interstitial Molecular Oxygen in Silicate Glasses?[END_REF] All discussions agree that upon cooling charges are frozen inside the matrix, [START_REF] Mukherjee | Dynamics of Second-Harmonic Generation in Fused Silica[END_REF][START_REF] Alley | Secondary Ion Mass Spectrometry Study of Space-Charge Formation in Thermally Poled Fused Silica[END_REF][START_REF] Quiquempois | Model of Charge Migration during Thermal Poling in Silica Glasses: Evidence of a Voltage Threshold for the Onset of a Second-Order Nonlinearity[END_REF] inducing a strong static electric field in the glass, which can reach values up to 0.1-1 GV/m and be stable for years in some glass matrix. [START_REF] Myers | Large Second-Order Nonlinearity in Poled Fused Silica[END_REF][START_REF] Kazansky | Thermally Poled Glass: Frozen-in Electric Field Or Oriented Dipoles?[END_REF][START_REF] Dussauze | Large Second-Harmonic Generation of Thermally Poled Sodium Borophosphate Glasses[END_REF] The first use of thermal poling was for glass to metal sealing [START_REF] Wallis | Field Assisted Glass-Metal Sealing[END_REF] but it was then found to be useful in nonlinear optics since the formation of the strong electric field effectively breaks the glass' centrosymmetry. This process disrupts the glass' initial isotropic nature inducing second-order nonlinear optical properties such as second harmonic generation (SHG) [START_REF] Myers | Large Second-Order Nonlinearity in Poled Fused Silica[END_REF][START_REF] Bethea | Electric Field Induced Second Harmonic Generation in Glass[END_REF] through an electrooptical effect called electric field induced second harmonic generation (EFISH). [START_REF] Kazansky | Thermally Poled Glass: Frozen-in Electric Field Or Oriented Dipoles?[END_REF] More recently the poling-induced electric field itself has been proven useful for enhancing surface reactivity in bioglasses and ceramics to promote bone growth and bonding. [START_REF] Yamashita | Acceleration and Deceleration of Bone-Like Crystal Growth on Ceramic Hydroxyapatite by Electric Poling[END_REF][START_REF] Obata | Electrical Polarization of Bioactive Glass and Assessment of their in Vitro Apatite Deposition[END_REF][START_REF] Nakamura | Electrostatic Surface Charge Acceleration of Bone Ingrowth of Porous Hydroxyapatite/ß-Tricalcium Phosphate Ceramics[END_REF] Thermal poling has also been shown to enable control of a material's properties at a micrometer scale. The process has been demonstrated to work up to submicronic scales by mean of patterned electrodes [START_REF] Lipovskii | Electric Field Imprinting of Sub-Micron Patterns in Glass-Metal Nanocomposites[END_REF][START_REF] Chervinskii | Formation and 2D-Patterning of Silver Nanoisland Film using Thermal Poling and Out-Diffusion from Glass[END_REF][START_REF] Lipovskii | Imprinting Phase/Amplitude Patterns in Glasses with Thermal Poling[END_REF][START_REF] Redkov | Nanoprofiling of Alkali-Silicate Glasses by Thermal Poling[END_REF][START_REF] Brunkov | Submicron-Resolved Relief Formation in Poled Glasses and Glass-Metal Nanocomposites[END_REF] but to date, only the optical properties and surface relief have been studied. In this letter we demonstrate that the surface reactivity of a borosilicate glass can be precisely controlled at the micrometer scale by use of patterned electrodes.

Borosilicate glasses of composition SiO 2 39%, B 2 O 3 51% and Na 2 O 10% were prepared as described elsewhere. [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF] The glass slab was then cut in one-millimeter-thick samples which were optically polished. Glasses were visually inspected and showed no sign of inhomogeneity or phase separation.

A microscope glass slide with a 100 nm thick ITO layer deposited on it was used as the anode.

The ITO layer was structured by laser ablation using a 1064 nm nanosecond yttrium aluminum garnet (YAG) laser. Various patterns were written on the surface by moving the sample with a motorized stage (X, Y) under the laser beam. AFM measurements performed in simple peak force taping mode, not presented here, show that the 100 nm thick ITO layer is entirely removed from the glass surface following laser ablation ensuring no electronic conductivity in these regions. Rectangles 40x60 μm 2 were written on the ITO electrode as this dimension allows spatial mapping over this area using μ-SHG, μ-Raman and μ-IR spectroscopy.

The glass sample was put between the patterned electrode at the anode and a silicon wafer at the cathode and placed in the poling cell. The treatment took place in a nitrogen atmosphere and the sample was heated at 300°C. After 10 minutes, when a constant temperature was reached, a DC bias of 3000 V was applied across the sample for 30 minutes. The sample was then brought back to room temperature and only then the DC bias was removed.

To prevent any reaction of the poled glass with the laboratory atmosphere, the cell was placed in a glove bag, filled with nitrogen, once the poling was performed. The sample was taken out of the poling cell and placed in a controlled atmosphere cell fitting under an optical microscope. To evaluate the efficiency of the thermal poling, the sample was first studied under an optical microscope to examine the patterned electrode's transfer fidelity to the glass' poled surface. The pattern is precisely transferred to the glass surface through the electrostatic imprint process taking place during poling, as observed on figure 1-(a). [START_REF] Takagi | Electrostatic Imprint Process for Glass[END_REF] It has been documented that an efficient thermal poling breaks the centrosymmetry of the glass by inducing a strong static electric field in the near anode surface. [START_REF] Myers | Large Second-Order Nonlinearity in Poled Fused Silica[END_REF] This electric field contributes to SHG in the glass through the electro-optical effect EFISH mentioned earlier. To evaluate the effectiveness of the poling at the micrometer scale, we used a SHG microscope based on a modified micro-Raman spectrometer HR800 equipped with a 1064 nm picosecond laser, described elsewhere. [START_REF] Rodriguez | Hyper-Raman Macroand Micro-Spectroscopy in Materials: Towards High Quality Signals and Good Spatial Resolution[END_REF] A SHG map of one of the rectangle imprinted on the glass surface was obtained with a 50x objective, using a radial polarized doughnut shaped beam profile that probes the longitudinal (along z) SHG contribution, Figure 1-b. It is important to define the referential in which our SHG measurements are made. In this article, in-plane components correspond to a signal located in the plane of the glass surface (x-y plane) while longitudinal components are perpendicular to the x-y plane, i.e. along the z-axis.

Figure 1. (a) Optical micrograph of a rectangle inscribed on the surface after poling, (b) corresponding µ-SHG map across the rectangle imprinted on the sample

The SHG active zone is spatially located around the rectangle. The maximum of intensity in the active zone is 10 times higher than the background measure inside the rectangle pattern. The intensity variation between the ITO-free area and the poled area and the location of the SHG active zone are in agreement with the literature. [START_REF] Yang | Large Scale Micro-Structured Optical Second Harmonic Generation Response Imprinted on Glass Surface by Thermal Poling[END_REF] These measurements however differ with our results previously published for niobium borophosphate glasses. [START_REF] Dussauze | Accurate Second Harmonic Generation Microimprinting in Glassy Oxide Materials[END_REF] In this other study, we could observe two contributions to the SHG signal with the longitudinal polarization that were located on each side of the edges of the patterns. In the case of the borosilicate glass presented here, the second contribution is not clearly observed. The second major difference with previous literature results is that the SHG active zone is present over distances as wide as 10 μm, while on the niobium borophosphate glasses, the signal was confined to spatial regions of less than 5 μm. The third major difference in our study is that components of the SHG signal in the plane of the substrate are not contributing as much to the SHG signal and have considerably lower intensities.

The SHG response as depicted on figure 1 is however clearly structured and is linked to an edge effects and a higher density of charges induced in the border of the patterns. In a classical thermal poling treatment, carried out without structured electrodes, the electric field is perfectly perpendicular to the surface thus only giving a longitudinal and uniform intensity of the SHG across the poled surface. By removing strips of ITO on the electrode, a field enhancement phenomenon seems to be taking place by changing the charge density along the glass surface as well as promoting charge displacement not only along the z-axis but also in the x-y plane of the glass (the x-y plane being in the plane of the glass surface and the z axis going inside the sample). Along the patterned area, an increase of two order of magnitude in the charge concentration is observed, thus giving more trapped charges after poling and enhancing the SHG in these areas. [START_REF] Dussauze | Accurate Second Harmonic Generation Microimprinting in Glassy Oxide Materials[END_REF] The in-plane poling contribution which should give the other contribution to the electric field is greatly related to the ITO-ablated area and to surface current formation. The overall SHG intensity is smaller in thermal poling of borosilicate glasses compared to borophosphate niobium glasses. The geometry of the electro-optical anisotropy induced in both glasses is different and it is possible that depending on the glass composition, surface currents responsible for this effect are accessible at different ranges in the structured areas. The area over which the electric field is going to be induced and structure would therefore be different, therefore leading to various thickness and intensity of the SONL active area.

To evaluate the departure/migration of sodium from the poled region, vibrational spectroscopy is suitable in this glass as sodium migration leads to a necessary re-arrangement of the glass matrix which greatly impacts the borate network. [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF][START_REF] Möncke | Thermal Poling Induced Structural Changes in Sodium Borosilicate Glasses[END_REF] A µ-IR spectroscopic study was performed using a PerkinElmer Spotlight 400 spectrometer under air with a resolution of 4 cm -1 between 4000 and 750 cm -1 with a 1 cm -1 resolution. The borosilicate glass used here lies on the boric acid anomaly and its structure was fully described elsewhere. [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF][START_REF] Möncke | Thermal Poling Induced Structural Changes in Sodium Borosilicate Glasses[END_REF][START_REF] Möncke | Thermal History of a Low Alkali Borosilicate Glass Probed by Infrared and Raman Spectroscopy[END_REF] Its glass network is made of reticulated silica tetrahedra and borate groups close to pentaborate entities. Every sodium added to the glass is present in the vicinity of a 4-coordinated boron tetrahedron acting as a charge compensator.

The remaining boron entities are 3-coordinated (where denotes a bridging oxygen) triangular units in rings and non-rings units.

Following thermal poling, µ-IR reflectance spectroscopy was used to probe the structural

Figure 2. Optical micrographs of the surface (a), spectra taken on positions A, B & C on the optical micrographs and IR map (b) and corresponding micro-IR map taken on the blue rectangle presents on the optical micrograph, presenting the intensity distribution of the band between 1200 and 1500 cm -1 (c)

All spectra presented in this figure were normalized to the intensity of the band peaking at 1075 cm -1 , attributed to the asymmetric stretching vibrations of Q 4 siliconoxygen tetrahedra, i.e.

fully cross-linked SiO 4 tetrahedra. [START_REF] Tenney | Vibrational Spectra of Vapor-Deposited Binary Borosilicate Glasses[END_REF][START_REF] Bell | Structure and Phonon Spectra of SiO2, B2O3 and Mixed SiO2B2O3 Glasses[END_REF][START_REF] Kamitsos | Infrared-Reflectance Spectra of Heat-Treated Sol-Gel-Derived Silica[END_REF] The band peaking at 910 cm -1 is attributed to the asymmetric stretching vibrational mode of tetrahedra, i.e. a boron tetrahedron with a neighboring sodium cation to balance its charge. [START_REF] Möncke | Thermal Poling Induced Structural Changes in Sodium Borosilicate Glasses[END_REF][START_REF] Kamitsos | Infrared Reflectance Spectra of Lithium Borate Glasses[END_REF] The boron network presents another contribution between 1250 and 1500 cm -1 that corresponds to an asymmetric stretching vibrational mode of triangular units in ring and non-ring configurations. [START_REF] Möncke | Thermal History of a Low Alkali Borosilicate Glass Probed by Infrared and Raman Spectroscopy[END_REF] The IR spectrum Changes observed in the regions where thermal poling was effectively taking place can be directly linked to the departure of sodium cations towards the cathode. Absence of charge compensators in the vicinity of tetrahedra forces them to re-arrange into triangular units, thus forming a network close to pure B 2 O 3 which have a single band in IR-spectroscopy. [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF][START_REF] Möncke | Thermal Poling Induced Structural Changes in Sodium Borosilicate Glasses[END_REF] In the process it should be noted that the silica tetrahedra are not impacted by the poling.

The structural changes observed in in IR spectroscopy indicates the departure of sodium from the vicinity of the tetrahedra and indirectly indicates the formation of molecular oxygen. It is however difficult to conclude on the intermediate reaction and on the nature of the oxygen specie during this process. Two hypothesis can be considered, (i) the creation of oxygen anions or (ii) the creation of peroxide radicals. The first possibility implies the breakage of a bonds and the formation of oxygen anions which recombine following a redox process to form molecular oxygen. The second possibility is the breakage of a or bond followed by the release of one electron and the formation of peroxide radicals which will then combine to form molecular oxygen. [START_REF] Redkov | How does Thermal Poling Produce Interstitial Molecular Oxygen in Silicate Glasses?[END_REF] In our case, we do not rule out any of these two possibilities but conclusions cannot easily be drawn and the question remains open.

As shown in our previous article, once poled, the formation of a new structure, associated with a strong internal electric field enhanced the glass' reactivity towards atmospheric water. All measurements shown so far were carried out before the glass reacted with the laboratory atmosphere, either under controlled atmosphere or in air before any reaction. To evaluate the glass surface's reactivity, the sample was let free to react with its surrounding environment until it started to show signs of reaction as observed previously. [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF] One should keep in mind that the kinetic of this process is highly dependent on the humidity content of the laboratory and that this parameter is not controlled in this study. triborate group with one and to triangular units in rings. [START_REF] Konijnendijk | The Structure of Borosilicate Glasses[END_REF][START_REF] Furukawa | Raman Spectroscopic Investigation of the Structure of Silicate Glasses. III. Raman Intensities and Structural Units in Sodium Silicate Glasses[END_REF] At lower wavenumbers, a large envelope can be attributed to mixed stretching and bending vibrations from the silicate network. [START_REF] Brethous | Etudes Par Spectroscopie Raman Et Par RMN Des Verres Du Système B2O3 SiO2 Li2O[END_REF] In addition to the mode of the glass, several contributions from boric acid, H 3 BO 3 , as seen previously in the literature, [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF] are present. The bending mode of the O-B-O bound is observed at 500 cm -1 , the B-O symmetrical and antisymetrical stretching vibrational mode at 880 cm -1 and 1384 cm -1 and the bending mode of B-OH bonds at 1172 cm -1 are all present. The two last contributions at 3165 and 3251 cm -1 are attributed to O-H stretching vibrational modes. [START_REF] Krishnan | The Raman Spectrum of Boric Acid[END_REF] Presence of boric acid is easily explained, as it is known that following the creation of the charged borate structure, atmospheric water is attracted to the surface of the glass, and then reacts with it through a leaching process to form boric acid. [START_REF] Lepicard | Surface Reactivity Control of a Borosilicate Glass using Thermal Poling[END_REF] Map (c) depicts the distribution of the integrated area under the main peak of boric acid at 880 cm -1 . From this map, it can be observed that boric acid is only present outside the pattern. The intensity of the integrated band is null across the pattern while outside of it, it is more than an order of magnitude stronger. Boric acid is thought to be dissolved in water at the surface of the glass as it is known to be soluble in water even at room temperature. [START_REF] Thomas | Determination of the H3BO3 Concentration in Fluid and Melt Inclusions in Granite Pegmatites by Laser Raman Microprobe Spectroscopy[END_REF] Infrared reflectance spectroscopy (bottom row) allows further confirmation of the information observed with Raman spectroscopy. Spectra recorded in areas that have reacted with the atmosphere present a distinctly different signature from either the base glass or post-poled glass, illustrated in figure 3 -(d). A large contribution from asymmetric stretching vibration of OH groups is observed between 3000 and 3500 cm -1 . The vibrations originating from the glass network are also changed with a large decrease of the triangular units. However, as a large water band is present in the spectrum, it is hard to draw conclusions on the glass network.

Infrared reflectance measurements only probe the first few microns of a surface and the water band thus masks the contribution of the sub-surface glass network. Such a spectrum can only give valid information on the presence of water at the surface. A map of the distribution of this water band is shown on part € of figure 3. The infrared map was recorded on a larger zone to image four squares (one fully and the three others partially). Water presence is correlated to the areas where changes occur upon poling while inside the patterns, no water signature is observed.

The important information to remember from this IR-map is that inside the pattern, the OH band is null whereas outside of it, it strongly increases, thus showing the unique spatial selectivity of the surface reactivity enhancement imparted by the μ-poling process.

In conclusion, the use of a patterned electrode during thermal poling has been proven as an effective way to imprint spatially specific designs, control the location of the induced electric field, control the scale over which structural modifications take place and finally control the reactivity on a glass' surface. It is also shown that with the use of patterned electrodes, an enhancement of the SHG signal at the border of the patterns is observed due to a confinement effect of the electric field. Moreover, as observed in infrared spectroscopy, the glass structure is efficiently modified at a micrometer scale around the pattern. A poling-induced charged surface structure was formed and tailored on a micrometric scale. The poled area also exhibited enhanced surface reactivity towards atmospheric water. This reactivity was only enhanced on the effectively poled area, corresponding to areas in close contact with ITO upon poling. These new results allow to foresee the use of a micro-poling technique to tailor physical and chemical properties of glasses and to use it for a variety of applications, ranging from photonics to lab-ona-chip devices.

  changes close to the glass' surface inside and outside the patterns. An optical micrograph of several patterns imprinted on the glass is shown on part (a) of figure 2, as well as three individual spectra recorded on positions A, B & C, shown on the optical micrograph, and the corresponding IR-map showing the integrated area linked to triangular units asymmetric stretching mode [1200 and 1550 cm -1 ] distribution.

  taken inside the pattern, at position A, presents the same signature as the unpoled base glass, showing that poling was not effective in this area. Now looking at the IR spectra taken outside the patterns, positions B and C, on figure 2 (b) several changes should be highlighted. The most drastic change concerns the signature of the triangular units which, in addition to its large increase, goes from a double band to a single band. Simultaneously, the band of the tetrahedra decreases in intensity. The IR map (figure 1-c) taken on the highlighted blue rectangle of the optical micrograph (figure 1-a) shows the intensity distribution of the band around a pattern. It is observed that inside the pattern the contribution of this group is highly lowered compared to its surroundings. This map also shows that the structural change taking place in the poled region (outside the rectangle) is homogeneous while the region inside the rectangle is left unchanged.

Figure 3 .Figure 3

 33 Figure 3. Optical micrograph of the glass surface after exposure to atmosphere (a), Raman spectrum taken outside of a pattern after exposure to atmosphere (b), Raman map recorded around the pattern presented on the optical micrograph, the intensity of the band of boric acid peaking at 880 cm -1 was imaged (c), IR reflectance spectrum taken outside a pattern after exposure to atmosphere (d) and IR map recorded around four squares showing the distribution of the intensity of the integrated band of asymmetric stretching vibration of OH groups between 3000 and 3500 cm -1 (e) Figure 3 focuses on the vibrational study of the surface after it reacted with the atmosphere. The

ACKNOWLEDGMENTS

This study has been carried out with financial support from the French State, managed by the French National Research Agency (ANR) in the frame of "the Investments for the future" Programme IdEx Bordeaux -LAPHIA (ANR-10-IDEX-03-02), and the French Aquitaine region [Grant 20121101025]. The authors (AL and KR) acknowledges the support of the National Science Foundation, award #DMR-1308946.


PhD Béatrice Siadou-Martin
email: beatrice.siadou-martin@univ-lorraine.fr

PhD David Vidal
email: david.vidal@univ-montp2.fr

PhD Juliet F Poujol
email: fpoujol@inseec.com

PhD John F Tanner
email: jtanner@odu.edu

SALESPEOPLE, FAIRNESS, AND BUYER SATISFACTION: WHAT ABOUT EMOTION?

Keywords: B2B relationships, emotions, justice

Purpose-While most studies focuses on rational decision in organizational settings, this research examines the emotional and rational dimension of the business-to-business (B2B) buying process and its influence on satisfaction through the integration of fairness and emotion theories. It thus broadens knowledge about the formation of satisfaction in buyerseller relationships, through an integration of justice and emotion theories.

. That is, we compared the proposed framework against two competing models: a non-mediated model and a saturated model that featured all possible causal paths.

Findings-The results show that positive emotions mediated the effect of fairness on satisfaction, though only partial meditation occurred between procedural fairness and satisfaction. Procedural fairness had both direct and indirect effects on satisfaction, through positive emotions.

Research limitations/implications-The findings have implications for both marketing scholars and managers. Buyers in business relationships are not completely rational, so B2B experts should acknowledge the influence of emotions in their theoretical models and sales strategies.

Practical implications-In addition to guaranteeing a "fair" outcome, sellers must ensure that buyers are subject only to fair procedures and that their salespeople generate positive emotions. Because buyers in business relationships are not completely rational, so B2B experts should acknowledge the influence of emotions in their sales strategies.

Originality/value-The mediating impact of emotion in the fairness-satisfaction relationship has not been explored in buyer-seller settings previously. Deconstructing satisfaction with the decision process into its cognitive and affective elements, we examine the emotional dimension of B2B buying process

Even in their work roles, people function as humans with all of the foibles and characteristics that suggests. This reality demands investigation of such elements as the role of human emotions in business-to-business (B2B) buying situations and sales interactions [START_REF] Bagozzi | The role of social and self-conscious emotions in the regulation of business-to-business relationships in salesperson-customer interactions[END_REF]. In contrast, most research focuses on rational decision making in organizational settings [START_REF] Tanner | Organizational buying theories: A bridge to relationships theory[END_REF], with a few exceptions that highlight the role of emotions in B2B interactions [START_REF] Andersen | Emotions, trust and relationship development in business relationships: A conceptual model for buyer-seller dyads[END_REF][START_REF] Tähtinen | The involvement and influence of emotions in problematic business relationships[END_REF][START_REF] Wang | Explaining buyers' responses to sellers' violation of trust[END_REF]. Emotions that emerge at the individual level strongly influence interactions at the interorganizational level and indicate several stimulating avenues for research [START_REF] Andersen | Emotions, trust and relationship development in business relationships: A conceptual model for buyer-seller dyads[END_REF][START_REF] Tähtinen | The involvement and influence of emotions in problematic business relationships[END_REF]. For example, some studies address emotions provoked by conflict or negative experiences [START_REF] Wang | Explaining buyers' responses to sellers' violation of trust[END_REF], and others review the broader role of emotion for trust development [START_REF] Andersen | Emotions, trust and relationship development in business relationships: A conceptual model for buyer-seller dyads[END_REF].

In nearly all these studies though, satisfaction appears as the outcome of a cognitive process, in which people evaluate the (dis)confirmation of their expectations [START_REF] Oliver | A cognitive model of the antecedents and consequences of satisfaction decisions[END_REF].

Literature on satisfaction judgments also supports both affective and cognitive components [START_REF] Babin | The nature of satisfaction: an updated examination and analysis[END_REF]). Yet, we still need research to tease apart cognitive versus emotional reactions to buyer-seller interactions and how they lead to satisfaction. One method to deconstruct satisfaction into cognitive and affective elements is to apply the concept of fairness-or specifically, evaluative judgments of the appropriateness of the treatment a person receives [START_REF] Chebat | How emotions mediate the effects of perceived justice on loyalty in service recovery situations: an empirical study[END_REF])-because fairness is primarily a cognitive concept, consistent with existing (dis)confirmation models of (dis)satisfaction [START_REF] Oliver | A cognitive model of the antecedents and consequences of satisfaction decisions[END_REF]).

What's left in determining satisfaction may be attributable to emotions. Accordingly, by deconstructing satisfaction with the decision process into its cognitive and affective elements, we can examine the emotional dimension of B2B buying process. We then study the mediating effect of positive emotions on the link between perceived fairness (distributive and procedural) and buyers' satisfaction. In the next section, we present a conceptual background pertaining to emotions and fairness in B2B relationships, before we detail the methodology for our quantitative study. Finally, after we discuss the results, we outline some managerial implications and research directions.

Emotions in B2B relationships

The notion of affect is a set of psychological processes and has been defined as a set of internal emotional states of positive or negative valence, which include the moods and emotions [START_REF] Westbrook | Product/consumption-based affective responses and postpurchase processes[END_REF]. There is no universally accepted definition of emotions, there are generally conceptualized as mental states resulting from the assessment of an event expressed positively or negatively [START_REF] Donada | Emotions in outsourcing. An empirical study in the hotel industry[END_REF]. Research in B-to-C show that emotions influence many aspects of consumer behaviours: Positive emotions increase consumer satisfaction while negative emotions cause the opposite effect [START_REF] Westbrook | Product/consumption-based affective responses and postpurchase processes[END_REF][START_REF] Westbrook | The dimensionality of consumption emotion patterns and consumer satisfaction[END_REF].

Although emotions are today recognized as pivotal variables in the explanation of the consumer behaviour, their influence in B-to-B has been very little studied. However, research on this subject highlight the role of affective states in the interactions between firms and show that emotions can also shape behaviour, decision-making processes and the strategies of negotiation of professional buyers [START_REF] Andersen | Emotions, trust and relationship development in business relationships: A conceptual model for buyer-seller dyads[END_REF].

Unlike transactional exchanges, interorganizational relationships imply a long-term orientation and recurring interpersonal interactions across boundary spanners [START_REF] Dwyer | Developing buyer-seller relationships[END_REF][START_REF] Ford | The development of buyer-seller relationships in industrial markets[END_REF][START_REF] Håkansson | International marketing and purchasing of industrial goods: An interaction approach[END_REF]. From an economic perspective, most research investigates how cognitive processes shape these interfirm exchanges through their rational aspects (e.g., transaction costs, power, dependence, commitment;[START_REF] Bagozzi | The role of social and self-conscious emotions in the regulation of business-to-business relationships in salesperson-customer interactions[END_REF]. With the assumption that B2B buyers are not emotional or impulsive but rather actors who make rational decisions and choices on the basis of their collective decision processes [START_REF] Voss | Cutting through the clutter[END_REF], existing literature has neglected emotional factors that also can shape interorganizational relationships. Yet [START_REF] Bagozzi | The role of social and self-conscious emotions in the regulation of business-to-business relationships in salesperson-customer interactions[END_REF] and [START_REF] Erevelles | The Role of Affect in Personal Selling and Sales Management[END_REF] maintain that business relationships contain both rational (cognitive processes) and emotional (affective processes) forces. Thus, including both sets of processes is necessary to understand business relationships. [START_REF] Bagozzi | The role of social and self-conscious emotions in the regulation of business-to-business relationships in salesperson-customer interactions[END_REF] even suggests that B2B regulatory mechanisms operate through intra-and interpersonal emotions. [START_REF] Andersen | Emotions, trust and relationship development in business relationships: A conceptual model for buyer-seller dyads[END_REF] further speculate that emotions, though they are individual variables, potentially affect partners' behaviors at both individual and organizational levels. Similarly, [START_REF] Vidal | Eye for an eye: Examining retaliation in business-to-business relationships[END_REF] demonstrates that one specific emotion (anger) in a B2B context influences organizational behaviors. These studies, though not in the context of satisfaction, do illustrate the importance of emotions in understanding buyer behavior.

Because interorganizational relationships evolve through interaction sequences that generate specific emotions, Täthinen and Blois (2011) demonstrate that a wide range of human emotions (with the exception of love) are activated during interfirm interactions. Both positive (joy, empathy, pride, attachment, surprise) and negative (sadness, anger, fear, guilt, shame) emotions have significant consequences for participants' behavior and the relationships between their respective organizations.

Thus, research into interorganizational relationships suggests that affect, not just cognition, is a relevant study topic for the B2B marketing field and must be considered to understand the evolution of such relationships. To address understand business relationships as social interactions, we adopt a micro-level of analysis and examine both emotional and rational dimensions of business relationships. [START_REF] Kumar | The effects of supplier fairness on vulnerable resellers[END_REF] noted some twenty years ago that the construct of fairness in buyer/seller relationships was ambiguous and relatively underdeveloped.

Fairness in B2B

Broadly, fairness reflects a person's evaluative judgment of the appropriateness of his or her treatment by others [START_REF] Chebat | How emotions mediate the effects of perceived justice on loyalty in service recovery situations: an empirical study[END_REF]. Recently, research; consider four types of fairness in commercial relationships: distributive, procedural, informational and interpersonal (the last two were combined in what was first named "interactional fairness") [START_REF] Duffy | Engaging suppliers in CRM: The role of justice in buyer-supplier relationships[END_REF][START_REF] Hoppner | The intertwined relationships of power, justice and dependence[END_REF]. But the concept of fairness in examinations of buyerseller relationships consists of two distinct components: distributive fairness and procedural fairness [START_REF] Hoppner | The intertwined relationships of power, justice and dependence[END_REF]. Distributive fairness refers to the perception of how equitable the distribution of the outcomes from a relationship is relative to the inputs invested into a relationship. Procedural fairness corresponds to the perception of the fairness of the procedure followed by the partner to arrive at the decision.

Distributive fairness arose from social exchange theory, which emphasizes the role of equity for modeling subsequent interpersonal interactions. For example, channel research suggests that distributive fairness refers to the reseller's perception of the earnings and other outcomes it receives from its relationship with the supplier. Procedural fairness, in a channels setting, refers to the reseller's perception of the fairness of the supplier's procedures and processes [START_REF] Kumar | The effects of supplier fairness on vulnerable resellers[END_REF]. In a B2B setting, customers evaluate fairness on the basis of the salesperson's behavior, and to do so, they rely on two distinct categories of fairness: distributive fairness, or the fairness of outcomes received, and procedural fairness, or the fairness of a process [START_REF] Kumar | The effects of supplier fairness on vulnerable resellers[END_REF].

RESEARCH AND MODEL HYPOTHESES

Satisfaction with processes explains overall customer satisfaction more effectively than do the characteristics of the product itself [START_REF] Humphreys | Exploring the relative effects of salesperson interpersonal process attributes and technical product attributes on customer satisfaction[END_REF]. The importance of interpersonal processes and the prior research on emotions and interpersonal B2B interactions and relationships (e.g. [START_REF] Tähtinen | The involvement and influence of emotions in problematic business relationships[END_REF] suggest that buyers cannot separate emotion out of their evaluations of service quality. According to [START_REF] Liljander | Emotions in service satisfaction[END_REF], emotional components should be modeled as inputs to satisfaction; we predict specifically that emotional components mediate cognitive evaluations and therefore begin by addressing relationships between fairness and satisfaction.

In business-to-consumer (B2C) settings, the positive relationship between distributive fairness and consumer satisfaction is well established (e.g. [START_REF] Goodwin | Consumer responses to service failures: influence of procedural and interactional fairness perceptions[END_REF][START_REF] Tax | Customer evaluations of service complaint experiences: implications for relationship marketing[END_REF]. Several studies also document the importance of fairness in long-term cooperation between organizations [START_REF] Jap | Pie sharing" in complex collaboration contexts[END_REF], particularly as a critierion for assessing overall relationship satisfaction [START_REF] Brown | The roles played by interorganizational contracts and justice in marketing channel relationships[END_REF]. Therefore, we hypothesize: H1: Distributive fairness has a positive influence on a buyer's satisfaction with the selling firm, such that buyers who report higher levels of fairness also report higher levels of satisfaction.

In marketing channel literature, procedural fairness is commonly defined as a "reseller's perception of the fairness of the supplier's procedures and processes in relation to its resellers" (Kumar, Scheer, and Steenkamp 1995, , p. 55). In a study examining the different aspects of service recovery policies, [START_REF] Clemmer | An investigation into the relationship of fairness and customer satisfaction with services[END_REF] identifies flexibility, waiting time, and efficiency as elements of procedural fairness. Furthermore, many B2C examples reveal that procedural fairness affects post-complaint behavior, such that consumers who consider procedures and policies fair are more likely to be satisfied (e.g. [START_REF] Saxby | Measuring consumer perceptions of procedural justice in a complaint context[END_REF][START_REF] Tax | Customer evaluations of service complaint experiences: implications for relationship marketing[END_REF]. This relationship also has been supported in B2B settings [START_REF] Brown | The roles played by interorganizational contracts and justice in marketing channel relationships[END_REF][START_REF] Kumar | The effects of supplier fairness on vulnerable resellers[END_REF]. In line with these conclusions, we hypothesize: H2: Procedural fairness has a positive influence on the buying firm's satisfaction with the selling firm, such that when processes appear more just, satisfaction increases.

Consumer research also has examined emotion in satisfaction judgments (e.g., [START_REF] Andreassen | Antecedents to satisfaction with service recovery[END_REF] and [START_REF] Smith | The effect of customers' emotional responses to service failures on their recovery effort evaluations and satisfaction judgments[END_REF] suggest that emotional responses have a distinct influence on satisfaction judgments, even after accounting for cognitive antecedents (e.g., perceived fairness). Thus, including emotions in satisfaction models increases the amount of variance explained [START_REF] Kim | Crime and Punishment Examining Customers' Responses to Service Organizations' Penalties[END_REF].

Service recovery literature further implies that perceived fairness affects consumers' behavior through emotions (e.g., frustration, anger, happiness). According to [START_REF] Scher | Affect and the perception of unfairness[END_REF], people do not calculate fairness but experience a fairness-related emotion and then react to it. This theoretical approach primarily is based on affect control theory (ACT), which states that people who are treated fairly experience positive emotions [START_REF] Homans | Social Behavior: Its Elementary Forms[END_REF]). In a review of studies related to the effects of fairness on emotions in contexts other than service recovery, [START_REF] Chebat | How emotions mediate the effects of perceived justice on loyalty in service recovery situations: an empirical study[END_REF] reveal that emotions are a way consumers cope with (in)fairness. Most studies concur that people who perceive the outcome as fair are ''satisfied'' [START_REF] Hegtvedt | The effects of relationship structure on emotional responses to inequity[END_REF][START_REF] Sprecher | How men and women expect to feel and behave in response to inequity in close relationships[END_REF]). In bargaining situations, ''the fairer individuals view their own outcome, the less likely they are to express general negative feelings and the more likely they are to express satisfaction" (Hegtvedt and Killian 1999, , p. 296).

The emotional effect of the procedural dimension of fairness is less well documented. [START_REF] Chebat | How emotions mediate the effects of perceived justice on loyalty in service recovery situations: an empirical study[END_REF] proposed emotions as mediating the effects of fairness on customer loyalty in service recovery. Following this lead, [START_REF] Dayan | Perceived justice and customer loyalty in the retail banking sector in the UAE[END_REF] confirmed the mediating effect of positive emotions between procedural fairness and exit or loyal consumer behavior, calling for investigations into the procedural component of fairness. Little research has done so, particularly in B2b and more importantly, in considering the relative influence of both distributive and procedural fairness. While we concur that the effects of procedural fairness should be mediated by emotions, distributive fairness may be less likely to be mediated by positive emotions. In this research we propose then to examine two paths leading to customer satisfaction: a rational path traditionally considered in B-to-B setting with distributive fairness that directly impact buyer's satisfaction; and an emotional path where emotion plays a mediator role between procedural fairness and buyer's satisfaction. Therefore, we propose the following hypotheses: H3: Positive buyer emotions do not mediate the influence of distributive fairness on the buyer's satisfaction. H4: Positive buyer emotions mediate the influence of procedural fairness on the buyer's satisfaction.

Research model

Figure 1 presents the research model and proposed hypotheses. Stated simply, we propose that fairness has both a direct effect on satisfaction and an indirect effect only for procedural fairness on satisfaction through positive emotions.

- -----------------------Place Figure 1 about here ------------------------

METHODOLOGY

Data collection

This research used a sample of buyers working in the bio-diagnostic sector in France. This sector offers an appealing setting because of the nature of the relationship between the buyer and the key account manager. The selling process usually entails long-term negotiations to build a unique selling proposition for customers (covering products, services, financial terms, and so on) and persists in providing after-sale services. These suppliers offer their customers significant information about the probable evolution of the sector (e.g., practices, competences, technology). Salespeople consequently serve as the key contact point for buyers, before, during, and after purchase episodes. Because of the complex nature of these services, both salespeople and purchasers are closely involved in the commercial exchange.

Salespeople are supported, when needed, with the assistance of many product managers who specialize in a specific product line.

The questionnaire for this study was attached to an e-mail sent to active and knowledgeable buyers. Respondents provided their opinions about their firm's relationship with a major supplier of their choice, indicated the duration of the relationship, and specified the frequency of various contact methods.

In all, 220 buyers received invitations to participate in the online web survey. We received 130 usable questionnaires, for a response rate of 59%. Most respondents were men (62%), aged between 31-50 years (58%), who had worked in small enterprises (85.3%) as buyers for at least 6 years (61.1%). The questions had been translated from English to French by two native speakers (American and French), using a back-translation process to ensure equivalence across the two languages. A pretest suggested some minor changes to the wording, on the basis of comments by French-speaking experts.

The data collection used existing scales, adapted to this study setting (see Appendix for the items). Distributive and procedural fairness were estimated with items from scales provided by [START_REF] Kumar | The effects of supplier fairness on vulnerable resellers[END_REF]. Positive emotions were measured with the three-item scale by White and Yu [START_REF] White | Satisfaction emotions and consumer behavioral intentions[END_REF], which in turn reflects prior studies of consumption emotions [START_REF] Liljander | Emotions in service satisfaction[END_REF] and presents emotions along a continuum, from negative to neutral to positive valence. Other scales simply use a list of adjectives to describe an emotional state. A valence approach is more appropriate for our effort to induce respondents to recall emotions toward a relationship. Finally, to assess satisfaction, we used [START_REF] Cannon | Buyer-seller relationships in business markets[END_REF] scale. Respondents had to evaluate each item on five-point Likert scales ranging from "not agree at all" (1) to "totally agree" (5).

Measure reliability

The reliability and validity of the measures were tested using SPSS and AMOS. First to explore the possibility of non-response bias, the responses of early and late respondents were compared using ANOVA. No differences in the mean scores of the variables were found, suggesting that non-response bias is not a major problem.

In accordance with previous studies that validated the scales, we found one dimension for each construct except for the Procedural fairness for which two factors appears. We suppress all the items that did not have good communalities and were not correlated to the others. Only the themes knowledgeability and courteous behavior that corresponds more to the interactional fairness of procedural fairness were kept in this research. The KMO test agrees with these factor solutions, which accounts for more than 50% of total variance. The reliability of internal consistency was estimated with the alpha of Cronbach's alpha is good.

A confirmatory analysis was then carried out using AMOS and indicates a good convergent validity of the scale insofar as all items have Student's t scores higher than 1.96 and satisfactory goodness-of-fit indices. The results indicated acceptable standardized estimates and t-values; in Table 1, we provide the alpha values and intercorrelations.

- -----------------------Place Table 1 about here ------------------------According to the Fornell-Larcker criterion [START_REF] Fornell | Evaluating structural equation models with unobservable variables and measurement errors[END_REF], a construct is deemed discriminately valid if it shares more variance with its assigned indicators than with other latent variables. In statistical terms, this test compares the square root of AVE with the correlations among latent variables. The results presented in Table 2 demonstrate discriminant validity, since all diagonal elements are greater than the non-diagonal elements in the corresponding rows and columns.

- -----------------------Place Table 2 about here - -----------------------The measurement model produced the following fit statistics: ² = 101.86, df = 65, p < .01, ²/df = 1.56, goodness-of-fit index (GFI) = .90, adjusted goodness-of-fit index (AGFI) = .84, Tucker-Lewis index (TLI) = .95, confirmatory fit index (CFI) = .96, root mean residual (RMR) = .06, and root mean square error of approximation (RMSEA) = .06. Thus it offers a reasonably good representation of the variance-covariance matrix of our measures and can be considered suitable for substantive analysis and interpretation.

Hypotheses tests

With structural equation modeling, we determined that the final model yielded the following fit statistics: ² = 96.00, df = 65, p < .01, ²/df = 1.47, GFI = .91, AGFI = .85, TLI = .96, CFI = .97, RMR = .06, and RMSEA = .06. The model thus provides an acceptable representation of the data. In Table 3, we present the hypotheses tests and results. To address the mediating role of positive emotions, we followed the procedure proposed by [START_REF] Baron | The Moderator-Mediator Variable Distinction in Social Psychological Research: Conceptual, Strategic, and Statistical Considerations[END_REF]. That is, we compared the proposed framework against two competing models: a non-mediated model (M2), from which we excluded positive emotions, and a saturated model (M3) that featured all possible causal paths.

- -----------------------Place Table 3 about here ------------------------ [START_REF] Baron | The Moderator-Mediator Variable Distinction in Social Psychological Research: Conceptual, Strategic, and Statistical Considerations[END_REF] propose four conditions that must be satisfied to establish mediation. First, researchers must establish that there is an effect that can be mediated, by demonstrating that the independent variables (distributive and procedural fairness) relate significantly to the outcome (satisfaction). Our results confirm that distributive fairness and procedural fairness both relate significantly to satisfaction. Second, the independent variables (distributive and procedural fairness) must relate significantly to the hypothesized mediating variable (positive emotions). We find that distributive and procedural fairness is significantly associated with positive emotions. That is, positive emotions mediate the path from procedural and distributive fairness to satisfaction.

Third, we must demonstrate that the hypothesized mediating variables (positive emotions) significantly affect the outcome variable (satisfaction), as is the case in our study, because positive emotions have a significant impact on satisfaction.

Fourth, we evaluated the nature of the mediation by examining the effect of the hypothesized mediating variable (positive emotions) on the relations between exogenous (distributive and procedural fairness) and endogenous (satisfaction) variables. To do so, we compared the results for the non-mediated and the saturated models. Overall, the results indicate that positive emotions do not mediate the impact of distributive fairness on satisfaction, as hypothesized, but partially mediate the impact of procedural fairness on satisfaction (i.e., the path between these variables becomes weaker when positive emotions are included).

RESULTS AND DISCUSSION

Regarding the mediating effect of positive emotions, our results offer support for the proposed relationships. The proposed model assumes that positive emotions mediate the effects of procedural fairness on satisfaction, whereas only partial meditation arose between procedural fairness and satisfaction. As proposed, however, distributive fairness is not mediated by positive emotions in its effect on satisfaction. Thus, fairness does offer a lens through which the effects of cognitive and emotional evaluations can be understood when individuals participate in organizational buying roles. In particular, distributive fairness arises from a purely rational evaluation of the exchange relationship and is not shaped by the emotional reactions of exchange partners. This outcome component directly affects satisfaction and does not elicit emotional reactions. We posit that distributive fairness, which is rooted in cognitive evaluations of relationships, is fundamentally dependent on rational forces.

In contrast, the impact of procedural fairness is partially mediated by positive emotions. This form thus affects satisfaction directly and indirectly through positive emotions, supporting our hypothesis regarding the moderating effect of emotions.

Together, the two main results suggest that the two components of fairness are significant drivers of customer satisfaction but with strongly divergent effects: Distributive fairness only operates directly; procedural fairness has both direct and indirect effects through positive emotions. That is, the rational outcomes derived from a relationship directly drive customer satisfaction, but the pathways by which these outcomes emerge is doubly important.

The procedural component of fairness both explains satisfaction and determines the emotions B2B customers feel, and it thus determines their level of satisfaction.

These findings are important for several reasons. First, our results are consistent with recent research that suggests emotions are key mediators of reactions to perceived fairness, along with attributions. Thus, we extend [START_REF] Chebat | How emotions mediate the effects of perceived justice on loyalty in service recovery situations: an empirical study[END_REF] and [START_REF] Schoefer | The impact of perceived justice on consumers' emotional responses to service complaint experiences[END_REF] contributions by showing that positive emotions partially mediate the relationship between perceived fairness and buyer satisfaction. This partial mediation may be a function of the B2B setting in which we conducted our study. As previously mentioned, prior research has focused on the individual roles of fairness and emotion on buyer satisfaction. This study is the first to demonstrate how fairness perceptions and emotions operate on B2B buyer satisfaction; by doing so, this study offers additional insights into the determinants of customer satisfaction.

Our findings also contribute to relationship marketing literature by documenting how salespersons can enhance relationships. Business buyers' positive emotions and satisfaction depend on their fairness perceptions, but only with regard to procedural fairness. These findings are consistent with existing literature that suggests procedural fairness is more important than distributive fairness for satisfaction. Consequently, economic rewards that flow from the relationship may be important, but the way the sale is realized is an even more powerful driver of customer satisfaction, as we demonstrate with this study.

In turn, firms might adopt several means to ensure that customers perceive "fair" treatment. Procedural fairness largely determines how customers assess relationships; to be perceived as a fair partner, the supplier therefore must develop fair procedures and policies.

More than the output, this process by which buyers acquire products and services can aid in establishing a long-term relationship. We therefore recommend that firms demonstrate an effective understanding of the supplier's environment and train their key account managers to exhibit only courteous attitudes toward buyers.

In addition to high quality service, sellers must ensure that buyers are treated the same way (e.g., unbiased information, identical procedures, flexibility), as well as with courtesy and respect. Because such procedures are executed by salespeople and other customer-facing personnel, firms must carefully instill the concept of customer satisfaction among these employees and train them in the proper delivery of service procedures. Formal training programs, well-established procedures, and ongoing constructive feedback can help ensure that employees, and thus the firm overall, deliver processes that will invoke perceptions of fairness.

Although the positive emotional responses derived from perceptions of the fairness of the exchange influence satisfaction judgments, their effect is weaker than the direct effect of procedural fairness on satisfaction, though still stronger than the direct effect of distributive fairness. This difference is not unimportant. As [START_REF] Ramaseshan | Effects of customer equity drivers on customer loyalty in B2B context[END_REF] explain it, relationship equity is of primary importance in B2B settings and salespeople should be ready and flexible to provide customization opportunities in all senses, especially in the way they interact with the buyer. With this finding, our study reiterates the services marketing literature mandate that "emotions should conceptually be included [into service satisfaction models] and combined with cognitive evaluations of service" (Liljander and Strandvik 1997, , p. 168). We know that some drivers of customer emotion in services such as the extend of employee smiling and the authenticity of the emotional labor display [START_REF] Hennig-Thurau | Are all smiles created equal? How emotional contagion and emotional labor affect service relationships[END_REF]. This knowledge can be transposed to sales but we can go further. As Smith and Bolton (2002, , p. 19) suggest, frontline service employees should be trained to "decode emotional cues … and to offer customized recovery efforts to customers who exhibit negative emotional cues." We posit that salespeople could correct, or even avoid, failed service encounters in real time by more effectively selling the way the buyer wants to buy. A recommendation of this study is then to select salespeople that have a high emotional intelligence [START_REF] Delcourt | Effects of perceived employee emotional competence on customer satisfaction and loyalty: The mediating role of rapport[END_REF]. Alternatively, companies could train salespeople to recognize and respond to emotions in order to generate positive emotion and drive customer satisfaction. The stake in BtoB -where the sales team interacts with the buying team -is to understand the development of collective emotional intelligence and how it impacts the relation and in particular individual and collective emotion.

Finally, when managers seek to understand and effectively apply the results of customer satisfaction surveys, this study suggests it is necessary to control explicitly for perceived fairness and emotions. While the Net Promoter Score has become widely accepted by businesses as a metric for understanding the depth of satisfaction [START_REF] Kristensen | Is the NPS a trustworthy performance measure?[END_REF], this study provides evidence that a different approach may be needed. When seeking to understand why customers are (dis)satisfied, managers must consider both process as procedural fairness and product as distributive fairness. As [START_REF] Tanner | Users' role in the purchase: their influence, satisfaction and desire to participate in the next purchase[END_REF] found in a study of organizational buyers, those who are dissatisfied with the purchase process are more likely to seek a bigger role in the next process, irrespective of product satisfaction. While we've long known that satisfaction with one purchase influences the next, those results combined with our study suggests not only that procedural fairness is more important but also how it can affect future decisions. Thus, our work provides significant insight into account management strategy, as salespeople and managers now have direction into how to set up not only stronger satisfaction but also more favorable buying centers.

Limitations and further research

Although this research sheds light on important issues, several limitations must be noted. First, the data we used to assess the proposed framework came from buyers operating in a single industry that is involved in highly complex purchases. This setting inevitably restricts the generalizability of our findings. Cross-validation in other contexts, such as commodities, services, and other product forms and purchasing contexts, would be required to broaden our understanding how fairness and emotions affect buyer satisfaction.

Second, our study underlines the importance of people and the procedural fairness of the exchange without examining the nature of the channel used by the salesperson. Looking at the impact of diverse nature of contact (email, telephone…) point on customer's emotion is an important track of research because of the (in)ability to gauge emotional responses to selling activities.

Third, we limit our analysis to a positive emotion and the distributive and procedural dimensions of fairness. Additional research could determine how different specific emotions also affect satisfaction.

Fourth, our model proposes a specific pattern of linear relationships between several variables. As suggested by Casado-Diaz, Mas-Ruis and Kasper (2007), the relationship between the variables we analyze might not be simple or straightforward. For example, with our temporal measure, we derived the mediating model post hoc; an in-situ study might uncover a more iterative relationship, to evaluate events, identify the emotions that result, and recognize the progression of additional events from a perspective that could alter the outcome.

If a buyer is happy (emotion) and satisfied (cognition) following an interaction, the next interaction likely differs from one that follows an encounter that left the buyer unhappy and dissatisfied. We adopt a holistic view [START_REF] Jüttner | Customer service experiences: Developing and applying a sequentialincident laddering technique[END_REF]) rather than an additive view because relationships and perceptions of satisfaction do not appear to be additive across interactions. However, previous encounters influence people's anticipation of the nature of future encounters and their behaviors within those encounters, which seemingly must affect perceptions of fairness and emotional responses. This study establishes a foundation for further investigations of this question.

Rather than our valence-based measure of emotions, another measurement approach could acknowledge the idiosyncratic elements of specific emotions (e.g., pleasure, happiness).

With this approach, different emotions have distinct impacts on satisfaction, so studying them might provide insights into the specific antecedents, phenomenology, and consequences of different emotions. Our conceptual model could be revised to include satisfaction and relationship concepts, such as loyalty, commitment, and trust ; for example, using the work of [START_REF] Yu | The contribution of emotional satisfaction to consumer loyalty[END_REF].

Finally, we gather static emotions in a dyad; without longitudinal data that allow for some dynamism, we know little about what factors influence the course of a relationship. We propose that if buyers feel positive emotions during service delivery, they might be more patient with the firm, even after a service failure. Further research should test this prediction.

As noted, because we gather static emotions in a dyad, future research should also consider disaggregating the buying center. Perspectives of process and outcomes vary by roles in the buying center (e.g. [START_REF] Tanner | Buyer perceptions of the purchase process and its effect on customer satisfaction[END_REF]) but this study was limited to a single contact. Future work should examine the buying center over time to discern the impact of emotions, perceptions of fairness, and other important variables related to customer satisfaction.

Conclusion

This study makes several important contributions to the understanding of customer satisfaction in a B2B setting. We demonstrate that positive emotions are important in understanding the effects of procedural fairness, a cognitive evaluation that is very important in determining satisfaction. Further, we demonstrate that positive emotions do not mediate evaluations regarding distributive fairness. These findings highlight the importance of salespeople and managerial policies that can enhance procedural fairness evaluations in order to lead to more positive emotions and higher customer satisfaction. Not only do these findings have practical implications for managing customer relationships and measuring satisfaction, the theoretical contributions are also important. This study offers the first look into the relative importance of both forms of fairness, as well as the first to tease apart the cognitive and emotional dimensions of customer evaluations in a B2B setting. While there is still much work to be done, this study offers a solid foundation for future study of cognition and emotion in organizational buying. Practitioner's summary :

The research show that economic rewards that flow from the relationship may be important, but the way the sale is realized is an even more powerful driver of customer satisfaction in Bto-B. Procedural fairness largely determines how customers assess relationships; to be perceived as a fair partner, the supplier therefore must develop fair procedures and policies. In turn, firms might adopt several means to ensure that customers perceive "fair" treatment.

More than the output, this process by which buyers acquire products and services can aid in establishing a long-term relationship. We therefore recommend that firms demonstrate an effective understanding of the supplier's environment and train their key account managers to exhibit only courteous attitudes toward buyers.

In addition to high quality service, sellers must ensure that buyers are treated the same way as well as with courtesy and respect. Because such procedures are executed by salespeople and other customer-facing personnel, firms must carefully instill the concept of customer satisfaction among these employees and train them in the proper delivery of service procedures. Formal training programs, well-established procedures, and ongoing constructive feedback can help ensure that employees, and thus the firm overall, deliver processes that will invoke perceptions of fairness.

Although the positive emotional responses derived from perceptions of the fairness of the exchange influence satisfaction judgments, their effect is weaker than the direct effect of procedural fairness on satisfaction, though still stronger than the direct effect of distributive fairness. This difference is not unimportant. As Ramaseshan, Rabbanee, and Tan Hsin Hui (2013) explain it, relationship equity is of primary importance in B2B settings and salespeople should be ready and flexible to provide customization opportunities in all senses, especially in the way they interact with the buyer.

This study underlines that as frontline service employees, salespeople in B-to-B should be trained to decode emotional cues. A recommendation of this study is then to select salespeople that have a high emotional intelligence. Alternatively, companies could train salespeople to recognize and respond to emotions in order to generate positive emotion and drive customer satisfaction. The stake in BtoB -where the sales team interacts with the buying team -is to understand the development of collective emotional intelligence and how it impacts the relation and in particular individual and collective emotion.

Finally, when managers seek to understand and effectively apply the results of customer satisfaction surveys, this study suggests it is necessary to control explicitly for perceived fairness and emotions. While the Net Promoter Score has become widely accepted by businesses as a metric for understanding the depth of satisfaction, this study provides evidence that a different approach may be needed. When seeking to understand why customers are (dis)satisfied, managers must consider both process as procedural fairness and product as distributive fairness. As [START_REF] Tanner | Users' role in the purchase: their influence, satisfaction and desire to participate in the next purchase[END_REF] found in a study of organizational buyers, those who are dissatisfied with the purchase process are more likely to seek a bigger role in the next process, irrespective of product satisfaction. While we've long known that satisfaction with one purchase influences the next, those results combined with our study suggests not only that procedural fairness is more important but also how it can affect future decisions. Thus, our work provides significant insight into account management strategy, as salespeople and managers now have direction into how to set up not only stronger satisfaction but also more favorable buying centers.

Table 1 :

 1 Reliability and intercorrelations of variables

		Mean	SD	1	2	3	4
	1. Distributive Fairness	8.85	2.41	.68
	2. Procedural Fairness	15.76	3.13	.11	.84
	3. Positive emotions	14.67	3.45	.20*	.69** .89
	4. Satisfaction	11.62	2.73	.22*	.62** .68** .89
		** Correlation is significant at the 0.01 level.

Table 2 :

 2 Psychometric Properties of the Measurement Model

	Constructs/Items	Original Sample	Standard Error	t-value	p-value	α	CR AVE	Root AVE
		Distributive Fairness		.73	.75	.46	.68
	DisFair1	.63	.16	5.09	.000
	DisFair2	.74	.24	5.15	.000
	DisFair3	.65	.24	5.09	.000
		Procedural Fairness		.85	.84	.59	.77
	ProcFair1	.50	.12	5.98	.000
	ProcFair2	.65	.09	8.48	.000
	ProcFair3	.94	.15	14.36	.000
	ProcFair4	.90	.15	8.48	.000
		Positive emotions		.88	.89	.68	.82
	PosEmo1	.83	.07	13.00	.000
	PosEmo2	.95	.08	13.00	.000
	PosEmo3	.90	.05	11.72	.000
	PosEmo4	.56	.08	6.92
			Satisfaction			.92	.89	.74	.86
	Sat1	.69	.06	10.70	.000
	Sat2	.94	.05	17.70	.000
	Sat3	.93	.13	10.70	.000
	Table 3: Hypotheses tests
	Hypotheses			M2 (non-mediated)	M3 (saturated)	Results
				Sd Coef.	t-value	Sd Coef.	t-value
	H1 Distributive fairness  Satisfaction	23	2.58	.18	2.14	No mediation
	H2 Procedural fairness  Satisfaction	.31	6.74	.33	3.21	Partial mediation
	H3 Distributive fairness  Positive emotions	-	-	.17	2.35	Not sig.
	H4 Procedural fairness  Positive emotions	-	-	.65	7.66	Sig
	H5 Positive emotions  Satisfaction	-	-	.42	4.14	Sig

Our firm is completely happy with this supplier If we had to do il all over again, we would still choose to use this supplier (Suppressed)

APPENDIX: List of questionnaire items

Distributive Fairness

How fair are your firm's outcomes and earnings compared to:

The effort and investment that we have made lo support the supplier's line (suppressed)

The roles and responsibilities the supplier assigns to your organization (suppressed) What other dealers in our industry earn What the supplier earns from sales through our dealership

The contributions your company makes to this supplier's marketing effort

Procedural Fairness

In relationships with their dealers, the supplier and their personnel


Marie Marie Daniela Dubois

Daniela Dubois
email: mariedaniela.dubois@gmail.com

Serge Pierre-Louis

Johalène Rabout

Cécile V Denis

Olivier Christophe

Sophie Susen

Jenny Goudemand

Pierre Boisseau

Rémi Neviere

Marie Daniela Dubois

Olivier Pierre-Louis

MSc Marie Daniéla Dubois

A Combination

come

the mother (I-2), the proband (II-2), and her sister (II-1) (►Fig. 1A). The proband was a woman affected by severe hemorrhagic manifestations. Her biological profile was evocative of VWD3: VWF:Ag = 1 to 5%, VWF:RCo =5%, FVIII:C= 2 to 3%, VWFpp = 6%, and a total absence of multimers assessed by electrophoresis (►Fig. 1B). She was usually treated with plasmaderived VWF concentrates. Interestingly, the VWFpp level in this patient was higher than expected for typical VWD3. The sister (II-3) who died from a nonhemorrhagic cause had the same clinical-biological profile as the proband. VWF sequencing revealed the presence of two causative genetic variants present in a heterozygous state (►Fig. 1C). The first one, p.(Val510=), is a previously unreported synonymous variant present in VWF propeptide, which is frequently found in Martinique, indicating the presence of a cluster. The second one, p.(Pro2145Thrfs*5), located on exon 37 has already been described in VWDtype 1 (VWD1) patients 2 and leads to a shift of the reading frame and the appearance of a stop codon. In addition to these two variants, five variants/polymorphisms (p.Ala631Val, p.Met740Ile, p.His817Gln, p.Asp1472His, and p.Arg2185Gln) previously described as non-or little deleterious in healthy populations have also been detected in this patient.

We next studied the mother and the father of the proband. The mother (I-2) had a normal biological assessment (VWF:Ag = 131%, VWF:RCo = 116%) and was asymptomatic without any bleeding. Sequencing of the mother's VWF gene revealed a single variant on the VWF mature subunit: the c.6432dup which results in a stop codon. This molecular abnormality described in the mother (I-2) is in favor of a status of transmitter of VWD3. The father (I-1) experienced excessive bleeding only as a result of trauma or surgery. Sequencing of the father's VWF gene led to the identification of one potential causative variant: p.(Val510 = ), and five polymorphisms previously identified in healthy individuals. The phenotype reported by the father is of particular interest as biological assays did not report any dissociation between VWF:RCo (10%) and VWF:Ag (12%), suggestive of VWD1 whereas the study of plasma VWF multimers showed a significant and uniform reduction in the percentage of high molecular weight forms and intermediate molecular weight forms (►Fig. 1B). This latter observation would be more compatible with a VWD type 2A (IIE) but the fact that the mutation is not in the D3 domain does not fit with such a picture. The second sister (II-1) of the proband has a clinico-biological phenotype similar to that of her father.

To understand better the effect of this new p.(Val510 = ) variant which appears to be relatively frequent in Martinique, we investigated 21 additional Martinican patients exhibiting the same variant. Patients' characteristics are indicated in ►Table 1. Median age was 63 years (interquartile range [IQR], 45-77) and 65% were female. The striking feature in these patients was a significantly increased VWFpp/VWF:Ag ratio with a median of 5.62 (IQR, 4.36-6,14).

Of note, this ratio could be calculated only for the 14 patients for whom the VWFpp level was measured. An increased VWFpp/VWF:Ag ratio (> 2.2) is indicative of an accelerated clearance of VWF. [START_REF] Sanders | WiN study group. Von Willebrand factor propeptide and the phenotypic classification of von Willebrand disease[END_REF] To further investigate this potential mechanism, we decided to perform desmopressin Another interesting feature associated with this mutation is the difficulty to really assign the patients to a very specific VWD type or subtype. As already mentioned for the father of our original family, the multimeric profile indicates a variable loss of high molecular weight multimers (►Fig. 3) but biological measurements did not show any discrepancy between VWF:Ag and VWF:RCo in most cases. However, since the main effect associated with this mutation appears to be the clearance defect, we propose to classify the patients as belonging to the subtype 1C.

In conclusion, VWF mutational analysis can be valuable for diagnosing and investigating the molecular etiology of VWD. [START_REF] Borràs | Unraveling the effect of silent, intronic andmissense mutations onVWF splicing: contribution of next generation sequencing in the study of mRNA[END_REF] The prediction softwares used (SpliceSiteFinder-like, MaxEntScan, GeneSplicer, NSPLICE, ESEFinder, RESCUE-ESE, and EX-SKIP) regarding c.1530G > A (p.(Val510 =)) interpreted the appearance of a donor site at 6 base pairs at the end of exon 13 which could potentially alter splicing. This synonymous mutation could therefore have an effect on VWF messenger ribonucleic acid processing, causing a shift in the reading frame and the appearance of a termination codon deletion of two codons. The American College of Medical Genetics and Genomics 5 predicted that this variant would probably be pathogenic. This study contributes to complete biological data on VWD, and more particularly on a population of Afro-Caribbean Martinican ancestry.

Note

Human samples were conserved in the Martinique biological bank (CeRBiM).

(

  DDAVP) intravenous infusion (0.3 μg/kg) in 4 patients with the p.(Val510=)mutation and wemeasured VWF:Ag, VWF: RCo, and FVIII:C levels at different time points after infusion. The administration of DDAVP prompted a significant increase in VWF:Ag, VWF:RCo, and FVIII:C levels in these 4 patients as well as in a control, a VWD1 patient with the p.(Pro1413Leu) mutation, which does not lead to any clearance defect (►Fig. 2). Sixty minutes after DDAVP injection, the levels of VWF and FVIII:C decreased sharply, returning to baseline levels between 4 and 6 hours post-DDAVP for 3 patients out of 4 carrying the p.(Val510 = ) mutation. One patient (represented by the black hexagons on the figure) proved to be a better responder to DDAVP than the other 3 patients (despite the same molecular profile). However, even in this patient, VWF:Ag and VWF:RCo decreased quicker than for the control. These results strongly suggest that the p.(Val510 =) variant induces an accelerated clearance of VWF.

Figure 1 :

 1 FIGURES LEGENDS

Figure 2 :

 2 Figure 2: VWF:Ag, VWF:RCo and FVIII:C levels after DDAVP administration

Figure 3 :

 3 Figure 3: Plasma VWF multimeric analysis of 3 patients with p.(Val510=)

  Figure 1

  Figure 2

Figure 3

 3 Figure 3

Table 1 :

 1 Clinical and laboratory characteristics of 23 Martinican patients with the p.Val510=)

	variant
	Characteristics	Patients p.(Val510=)
		(n=23)
	Age, years	63 (45-77)
	Females (%)	65
	Blood group non O (%)	30.43*
	FVIII:C (IU/dL)	26 (17-35)
	VWF:Ag (IU/dL)	20 (16-24)
	VWF:RCo (IU/dL)	14 (10-19)
	FVIII:C/VWF:Ag ratio	1.4 (1-1.67)
	VWF:RCo/VWF:Ag ratio	0.74 (0.5-0.94)
	VWFpp/VWF:Ag ratio 5.62 (4.36-6.14) * n= 7
	¶ n= 14
	Normal range for VWFpp/VWF:Ag 0.6-1.5

¶

Results are indicated as median (25th to 75th percentile) for age, FVIII:C, VWF:Ag, VWF:RCo, FVIII:C/VWF:Ag ratio, VWF:RCo/VWF:Ag ratio and VWFpp/VWF:Ag ratio.

Funding

This study was supported by Octapharma France and doctoral scholarships.

Conflict of Interest

None declared.