Use of α‐diketones as visible photoinitiators for the photocrosslinking of waterborne latex paints

The efficiency of several α‐diketones as visible light photoinitiators for the crosslinking of waterborne latex dispersions in the presence of acrylic monomers was evaluated. Among the eight α‐diketones studied, camphorquinone allows the fastest curing speed, and the curing of the acrylic waterborne coating is not affected by the presence of oxygen. The properties of the sunlight‐cured volatile organic compound (VOC)‐free pigmented paints prepared from the waterborne latex are as good or better than the equivalent conventional paint containing VOCs. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3171–3181, 2002     

Connecting Rheological Properties and Molecular Dynamics of Egg-Tempera Paints based on Egg Yolk

Egg-tempera painting is a pictorial technique widely used in the Middle Ages, although poorly studied in its physico-chemical aspects until now. Here we show how NMR relaxometry and rheology can be combined to probe egg-tempera paints and shed new light on their structure and behavior. Based on recipes of the 15th century, model formulations with egg yolk and green earth have been reproduced to characterize the physicochemical properties of this paint at the mesoscopic and macroscopic scales. The rheological measurements highlight a synergetic effect between green earth and egg yolk, induced by the interactions between them and the structural organisation of the system. ¹H NMR relaxometry emphasizes the presence and the structure of a network formed by the yolk and the pigment.     

Revealing the Distribution of Metal Carboxylates in Oil Paint from the Micro‐ to Nanoscale

Oil paints comprise pigments, drying oils, and additives that together confer desirable properties, but can react to form metal carboxylates (soaps) that may damage artworks over time. To obtain information on soap formation and aggregation, we introduce a new tapping‐mode measurement paradigm for the photothermal induced resonance (PTIR) technique that enables nanoscale IR spectroscopy and imaging on highly heterogenous and rough paint thin sections. PTIR is used in combination with μ‐computed tomography and IR microscopy to determine the distribution of metal carboxylates in a 23‐year old oil paint of known formulation. Results show that heterogeneous agglomerates of Al‐stearate and a Zn‐carboxylate complex with Zn‐stearate nano‐aggregates in proximity are distributed randomly in the paint. The gradients of zinc carboxylates are unrelated to the Al‐stearate distribution. These measurements open a new chemically sensitive nanoscale observation window on the distribution of metal soaps that can bring insights for understanding soap formation in oil paint.     

Lead replacement in the Molybdate Orange colour space

Due to the toxicological concerns over lead and lead compounds, there has been an increased trend to replace lead based materials in paint systems. Change in this instance has been driven primarily by Legislation and regulations, however in many cases global companies wish to show a unified approach and some have taken both a positive environmental marketing approach over their competitors with Lead free paints and a positive move on labour relations. The pigment manufactures have had the challenge to meet these requirements either from existing product ranges or to develop new pigments that are both commercially and technically viable. Due to the diverse application, systems and cost structures within General Industrial Paints no single product offers a universal solution. The higher performing pigments generally meet the higher specifications technically but because of their chemical complexity in processing and structure fail to achieve the lower comparable costs against Molybdate Oranges. With less complex pigment structures limitations are identified within the technical area. Additionally within the range of Molybdate Oranges differing grades are available treated to enhance temperature stability and chemical resistance or untreated to attain lower costs and increased saturation. For this reason paint producers have the choice of a single product within the mid performance area that would act as a compromise or alternatively select three products to fulfil all requirements with the associated logistic problems on supply, stock inventory and quality testing. Within the single product approach Pigment Orange 81 potentially offers the most flexible solution to the paint manufacturer in order to meet the volume market for Mid performance offering opacity, gloss, rheology, bleed resistance, good temperature stability and of great importance the ability to match the colour space occupied by Molybdate Orange. For the multiple pigment approach: High technical performance Pigment Orange 73 offering higher saturation than Molybdate Orange but with associated costs. Mid performance Pigment Orange 81 Cost effective Pigment Orange 34 and Pigment Orange 16 offer high saturation but limitations in durability.     

Effect of pigment concentration on NMR relaxometry in acrylic paints

Acrylic emulsion paint is among the most common media employed by 20th century artists. Since early acrylic paintings have begun to require the attention of conservators, scientists are working to characterize the properties of these paints to facilitate conservation efforts. In this study, we report an investigation of the physical and chemical properties of acrylic emulsion paints using single-sided NMR in conjunction with gloss measurements and scanning electron microscopy-energy dispersive spectrometry. Combining the data from these techniques gives insight into pigment-base interactions and the acrylic curing process, showing that as pigment concentration is increased in paints, the amount of acrylic base adsorbed to pigment particles increases, resulting in films with differing relaxation times. This research both emphasizes and contextualizes the utility of NMR relaxometry in studying cultural heritage objects and prompts further study into the effects of pigment concentration on the curing and conservation of paint films.     

Attenuated total reflection micro FTIR characterisation of pigment–binder interaction in reconstructed paint films

The interaction of pigments and binding media may result in the production of metal soaps on the surface of paintings which modifies their visible appearance and state of conservation. To characterise more fully the metal soaps found on paintings, several historically accurate oil and egg yolk tempera paint reconstructions made with different pigments and naturally aged for 10 years were submitted to attenuated total reflectance Fourier transform infrared (ATR FTIR) microspectroscopic analyses. Standard metal palmitates were synthesised and their ATR spectra recorded in order to help the identification of metal soaps. Among the different lead-based pigments, red lead and litharge seemed to produce a larger amount of carboxylates compared with lead white, Naples yellow and lead tin yellow paints. Oil and egg tempera litharge and red lead paints appeared to be degraded into lead carbonate, a phenomenon which has been observed for the first time. The formation of metal soaps was confirmed on both oil and egg tempera paints based on zinc, manganese and copper and in particular on azurite paints. ATR mapping analyses showed how the areas where copper carboxylates were present coincided with those in which azurite was converted into malachite. Furthermore, the key role played by manganese in the production of metals soaps on burnt and raw sienna and burnt and raw umber paints has been observed for the first time. The formation of copper, lead, manganese, cadmium and zinc metal soaps was also identified on egg tempera paint reconstructions even though, in this case, the overlapping of the spectral region of the amide II band with that of metal carboxylates made their identification difficult.     

A multipurpose compound for protective coatings

International regulations concerning the protection of both the environment and industrial workers have prompted paint manufacturers and end users to look for suitable replacements for traditional pigments.One of the aims of this investigation was to study the inhibitive properties of ferric benzoate-based paints in simulated marine corrosion condition (3% NaCl solution). Anticorrosive paints containing ferric benzoate were formulated and their performance was evaluated by accelerated (salt fog chamber) and electrochemical (corrosion potential and ionic resistance) tests.In addition, the action of ferric benzoate as a probable antifouling agent was studied through laboratory tests and marine exposure. Ferric benzoate hydrolyzes in seawater producing a pH decrease. In this sense, the effects of the pH and the anion benzoate dissolved in seawater and leached from an antifouling paint were evaluated on Balanus amphitrite nauplii. Although benzoate anion showed an intense narcotic effect on nauplii, the results of this research clearly demonstrated that the antifouling activity is due to the combined action of this anion and the pH decrease, i.e. there exists a synergic effect. Field trials confirmed laboratory assays; paints containing ferric benzoate were effective for inhibiting organism settlement and as corrosion of metal.     

新型光固化环氧丙烯酸酯乳液的制备及其防腐性能研究

将环氧树脂和非离子型表面活性剂在一定温度下与丙烯酸反应合成出改性环氧丙烯酸酯树脂,再利用相反转乳化法制备得到光固化水性环氧乳液。对该反应的原料种类、反应条件、以及乳化工艺进行了优化研究,并对不同条件下得到的乳液进行了综合性能评价。着重考察了环氧树脂的种类以及光引发剂的种类对乳液粒径、清漆膜电化学防腐性能和耐盐雾性能的影响。结果表明:选取环氧树脂E20,光引发剂IRGACURE651,酯化反应温度为105℃,反应时间3h,乳化温度为25℃~30℃,搅拌速度为800r/min时,制得的乳液稳定性和漆膜性能(包括漆膜的力学性能、电化学防腐性能和耐盐雾性能)最佳。     

Determination of elements in paints and paint scrapings by inductively coupled plasma atomic emission spectrometry using microwave assisted digestion

Summary Inductively coupled plasma atomic emission spectrometry (ICPAES) is applied to the determination of elements in paints and paint scrapings to evaluate potential occupational and environmental exposure to metals in paints. A microwave assisted digestion procedure of these materials using nitric and hydrofluoric acid mixtures under controlled pressure has been developed. The accuracy and repeatability of the recommended procedure for lead are documented and evaluated by analysing NIST SRM 1579 Powdered Lead Based Paint. Neutron activation analysis was applied as a reference method for other elements. A variety of industrial and domestic paints of different chemical composition were analysed. The advantages and limitations of microwave digestion of paints are discussed.     

Forensic discrimination of automotive paint samples using pyrolysis-gas chromatography-mass spectrometry with multivariate statistics

Analytical pyrolysis-gas chromatography (Py-GC) has been a standard method for the forensic analysis of automotive paint for a number of decades. Automotive paints are often identified by visual comparison of pyrograms for peak presence and intensities; however, such analyses can be subjective and time consuming. A preliminary investigation based on Py-GC-mass spectrometric analysis of 100 automobile paint samples of five different colors is presented. Designed experiments are employed to select pyrolysis conditions for adequate discrimination. Pattern recognition techniques including principal component analysis and canonical variates analysis are used to visualize clustering of pyrograms to validate comparisons between different automotive paint pyrograms. These methods have the potential to ease the interpretation task for data sets involving a large number of comparisons.     

随温度变化的"变色龙"

按组成和性质将示温涂料分为3类,让中学生了解示温涂料的用途,认识其核心物质-热致变色材料变色的原理。     

Study of behaviour on simulated daylight ageing of artists�� acrylic and poly(vinyl acetate) paint films

This work proposes a multi-method approach that combines advanced microscopy (SEM/EDX, AFM) and spectroscopy (UV-vis and FTIR) techniques. This approach not only characterises the behaviour of the additives of two commercial poly(vinyl acetate) (PVAc) and acrylic emulsion paints but also simultaneously characterises the changes in chemical composition and morphology observed in the paint films as a result of ageing due to the paints being exposed to an intense source of simulated daylight. In parallel, a series of mechanical tests were performed that correlate the chemical changes in composition and the changes observed in the films' mechanical properties. This work was a comparative study between both types of acrylic and PVAc paints. The results obtained are of great interest for the modern paint conservation field as they provide valuable information on the mid- and long-term behaviours of these synthetic paints.     

Zinc basic benzoate as eco-friendly steel corrosion inhibitor pigment for anticorrosive epoxy-coatings

The inhibitive properties of benzoate anion were known from many years ago but the employment of soluble compounds in anticorrosive paints is limited because their lixiviation would greatly increase coating permeability. However, it is possible to prepare insoluble metallic benzoates with certain cations. This paper describes the experimental procedure to prepare zinc basic benzoate to be employed in anticorrosive paints. The anticorrosive properties of zinc basic benzoate were assessed by electrochemical techniques (corrosion potential and linear polarization measurements). The nature of the compounds forming the protective layer was determined by different techniques, including spectroscopic ones. In a second stage, the anticorrosive properties of the pigment were evaluated by incorporating it in epoxy anticorrosive paints which, in turn, were evaluated by accelerated (salt spray and humidity tests) and electrochemical measurements (electrochemical impedance spectroscopy). The morphology and the nature of the protective layer grown under the paint film in the salt spray chamber was assessed by scanning electron microscopy (SEM) and UV–vis diffuse reflectance spectroscopy.

Experimental results showed that basic zinc benzoate was adequate to formulate epoxy anticorrosive paints with improved anticorrosive performance, especially with the water-borne binder.     

Identification of the chemical inventory of different paint types applied in nuclear facilities

The floors, concrete walls and many of the metal surfaces in nuclear power plant containments are coated with zinc primers or paint films to preserve the metal surfaces and simplify decontamination in the containment after the occurrence of a severe nuclear incident or accident. A chemical examination of paint films from different nuclear installations out of operation, as well as current operating ones, reveals that different types of paints are used whose composition can vary significantly. Results obtained for one type of paint at a certain nuclear site are in most cases unlikely to be comparable with sites painted with another type of paint. During normal operation and particularly during nuclear accidents, the paints will degrade under the high temperature, steam and irradiation influence. As paint and its degradation products can act as sources and depots for volatile iodine compounds, the type and aging conditions of the paint films will have a significant impact on the source term of the volatile fission product iodine. Thus, great care should be taken when extrapolating any results obtained for the interaction of radioactive iodine with one paint product to a different paint product. The main focus of the study is a comparison of the chemical profile of paint films applied in Swedish nuclear power plants. Teknopox Aqua V A, an epoxy paint recently used at Ringhals 2, and an emulsion paint used in the scrubber buildings of Ringhals 1–4 are compared with a paint film from Barsebäck nuclear power plant unit 1 that had been aged under real reactor conditions for 20 years. In addition, two paint films, an emulsion and a gloss paint, used in an international nuclear fuel reprocessing facility, are compared with the paints from the Swedish nuclear power plants.     

TG–DSC analysis applied to contemporary oil paints

Thermogravimetry coupled with differential scanning calorimetry (TG–DSC) has been commonly used in the field of conservation of Cultural Heritage for the study of art objects, especially for the characterisation of inorganic matrixes. In recent years, thermal analyses have been applied to the study of organic painting materials. The advantages of performing TG–DSC are linked to the fact that it is micro-destructive technique which does not require any treatment prior the analysis and provide useful information in relatively short time. The aim of this study is to describe the application of TG–DSC on the study of oil binders used in contemporary paints. Even if synthetic binders have become increasingly popular in the 20th century, many contemporary artists still prefer the more traditional media: drying oils. Although the wish of recalling traditional methods, much practical knowledge in paint preparation by mixing drying oil and pigments and in the behaviour of the mixture has been lost. This is mainly due to the different composition of contemporary materials in comparison with the traditional ones and may sometimes lead to different drying properties of the oil paint formulations and consequent problems in the art creation and conservation. For answer to this artistic need and in particular to the difficulties outlined by artists themselves in producing and employing oil paints, unpigmented and pigmented oil films were studied after a week, 1 and 2 years of natural drying under laboratory conditions. Thermal analyses were performed in air flow: the focus of this research was, in fact, to study the thermal and oxidative behaviours of young films for better understanding the very first processes leading to the formation of the film.     

The effect of TiO2 pigment on the performance of paratoluene sulphonic acid catalysed paint systems

The work has highlighted the importance of choosing the correct pigment for paratoluene sulphonic acid (PTSA) catalysed paints. Generally, surface treated TiO₂ grades which are basic in nature resulted in the best optical performance in comparison to acidic surface treated grades. The relative performance of the acidic surface treated grade can be improved by increasing the PTSA level in the paint or by using a resin with a higher acidity level. It is postulated that for these TiO₂ grades, the higher acid levels were found to give better steric repulsion. However, overall, the basic surface treated grade retained the best optical performance in PTSA catalysed paint systems.     

Dynamic headspace analysis of trace volatile components in polymeric materials by wide bore capillary gas chromatography

A novel dynamic headspace gas chromatographic system equipped with a wide bore capillary column was constructed for direct analysis of less volatile components in polymeric materials such as coating paints. With this system, the determination of typical paint additives such as hindered amine light stabilizers and ultraviolet absorbers could be carried out within a short time.     

Effects on the pigment distribution in paint formulations

Modern water-borne paints are applied in different areas ranging from high-gloss lacquers to flat, scrub-resistant interior paints. The pigment volume concentration (PVC) is one key-parameter adjusting the application properties. In this work formulations differing in the type of binder and dispersing agent were investigated by various techniques concerning the distribution of pigments in the liquid paints and films. The structure of the paints was analyzed by Remission Light Spectroscopy (RLS), Disc Centrifugation, Cryo-Replica Transmission Electron Microscopy (Cryo-TEM) and Cryo-Scanning Electron Microscopy (Cryo-SEM). The pigment distribution in the films was examined by means of Atomic Force Microscopy (AFM), TEM and RLS. The tendency of the pigments to form aggregates was found to depend on both: the type of binder and the dispersing agent. Only by adjusting the properties of the binder in combination with common dispersants it is possible to get well distributed TiO₂ particles within the paint. Correlation of application properties e.g. gloss and blocking to the microscopic structure is presented.     

The rheology of aqueous emulsions prepared by direct emulsification and phase inversion from a high viscosity alkyd resin

A comparison of the rheological properties of dispersions of an alkyd resin in water prepared by direct emulsification and phase inversion has been conducted. These dispersions have application as the base dispersion in the manufacture of the new generation of water based gloss paints. An experimental investigation of the effect of dispersed phase fraction, droplet size and dispersion age on the rheological properties of dispersions produced by each emulsification route has been carried out. The droplet size distributions of the dispersions are also characterised. It was found that phase inversion always gave a smaller droplet size distribution than direct emulsification. Surprisingly it was found that for a given dispersed phase fraction, the dispersions with a smaller droplet size, produced by the phase inversion route, have a lower zero shear rate viscosity than those produced by the direct emulsification route. The rheology of the direct emulsification samples was also observed to change with age, whilst with phase inversion samples the rheology was stable. It is proposed that this and other differences observed between the two methods of manufacture can be associated to the presence, or otherwise, of excess surfactant in the aqueous phase.     

Paint Formulation Using Water Based Binder and Property Studies

Vinyl acetate – Butyl acrylate (VAc-BuA) copolymer latices of various compositions were prepared by semicontinuous emulsion polymerization. The copolymer formed after removing the homopolymers was characterized by FTIR spectroscopy. Mechanical properties were studied by Universal Testing machine. Differential scanning calorimetry (DSC) study of copolymer showed single glass transition temperature (Tg) value confirming the absensce of graft and block copolymer. These copolymer latices were used as the binder in water based latex paint formulation. The paint prepared using 85/15 wt.% of VAc-BuA was found to give a better paint properties. Water based paints are generally easier to apply and clean up. The surface properties found to be superior compared to commercially used paint.