09.12.2014
The new resin is compatible with a wide range of epoxy, urethane and polyester acrylates making it easy for the formulator to enhance the performance of the coating or varnish. Surface photopatterning of organosilane self-assembled monolayers (SAM) has received increasing attention since its introduction 20 years ago. Photoacid-catalyzed sol-gel polymerization is now recognized as a powerful single-step synthetic approach to the synthesis of hybrid films, which can be distinguished from conventional sol-gel methods by higher reactivity and a solvent-free process.
In the present study, a novel single hybrid monomer combining a vinylether and trimethoxysilane groups in the same molecule was synthesized by chemoselective hydrosilation and subjected to UV-irradiation in the presence of a triarylsulfonium salt.
A difunctional methacrylate oligomer was mixed with a variable amount of a MAPTMS precursor in the presence of both a radical and a cationic photoinitiator. A dual UV-curing process inducing in a single step cationic photopolymerization and a photoinduced sol-gel process was used to obtain novel hybrid coatings. Nanocomposite materials prepared from radically photocurable hybrid sol?gel precursors have been widely developed within the last decade, especially to devise novel optical devices and coatings. In this work, the dual organic-–inorganic UV-curing of (meth)acrylate trimethoxysilane precursors is performed in one step through the association of a radical and a cationic photoinitiator. The synthesis and characterization of bridged polysilsesquioxane films was performed via a photoacid-catalyzed sol–gel method using a series of three precursors with different organic moiety structures.
Hybrid sol-gel films were prepared via a simultaneous organic-inorganic UV-curing process using a diaryl iodonium salt as a superacids' photogenerator. Hybrid sol-gel films were prepared via a simultaneous organic-inorganic UV-curing process using a diaryliodonium salt as a superacid photogenerator.
In this work, a novel one-step methodology for preparing hybrid sol-gel coatings has been investigated by UV irradiation of simple and commercial bifunctional hybrid precursors R'Si(OR)3, bearing both an organic epoxy function and alkoxysilane moieties, in presence of an aryl iodonium salt catalyst. A variety of CIPP products are enabling the rehabilitation, rather than excavation and replacement, of underground pipe for wastewater and drinking water.
This estimate of current annual resin usage and liner footage in the North American market helps underscore the potential for the CIPP portion of the composites market as its percentage of the pipe rehabilitation business grows. Cured-in-place pipe (CIPP) has been a growing subset of trenchless technology since its 1971 debut and is now a substantial market for composite materials (see Table 1, at left). Due largely to research and development on the part of various resin producers, CIPP structures can be designed to satisfy virtually any need for underground pipe rehabilitation, from industrial plants to potable water lines. The original pipe was first cleaned by a single pass from a jetter nozzle (pressurized water spray), but it was not thoroughly scrubbed, Inliner’s Yothers says, noting that the practice was avoided in this case to prevent further damage. The water used in the process was treated through a sequence of retention ponds before it was returned to the river. Liners that are impregnated with isopolyester or vinyl ester resins formulated for cure by UV light are not catalyzed, but instead they contain a photo-initiator that reacts to certain wavelengths of UV light.
Before the UV CIPP liner is installed, the damaged host pipe is thoroughly cleaned, flushed and inspected by video.
During the summer of 2012, the contractor also installed LightStream UV CIPP liners to repair damaged 14-, 18- and 20-inch (360-, 460- and 510-mm) diameter pipelines in the oil fields of Valdez, Alaska. In 2005, another UV advocate, Reline America (Saltville, Va.), purchased UV CIPP technology from Brandenburger GmbH (Landau, Pfalz, Germany), which developed one of the first UV-curable pipelining systems. Berolina typically mixes its own UV-curable vinyl ester and isophthalic polyester systems, using base resins from AOC or CCP Composites (N. UV cure not only simplifies installation, but it also is said to result in a tight fit between the CIPP liner and the host pipe, an important issue when liner crews are reconstructing service connections. This limitation, and the fact that many municipalities are now banning the use of styrenated resins for CIPP because of its odor and concerns about volatile organic compound (VOC) emissions, has prompted resin formulators to develop vinyl ester resins that replace styrene with an alternative reactive monomer to reduce or eliminate VOC emissions.
Because the sewer pipe is buried in a U-configuration, the leaking section was difficult to access. Another alternative to styrene-based systems, of course, is epoxy, which is also a 100 percent solids system. Perma-Liner Industries (Clearwater, Fla.) uses epoxy for its liners to eliminate emissions in the densely populated areas it typically serves, says Travis Bohm, business development manager.
HAP and VOC emissions are prohibited in, and UV-curable resins are not approved for, the drinking water pipeline repair. Herein we report for the first time a cost-efficient soft photopatterning technique affording amplified 3D multilayer structures. Driven by hydrophobic van der Waals interactions, a photoinduced self-assembly process occurs to afford a long-range ordered lamellar mesostructure, characterized by X-ray diffraction and transmission electron microscopy. Through the UV-decomposition of this photoacid generator, two acid-catalyzed processes occurred simultaneously: the cationic polymerization of the vinyl ether functions and the sol–gel polycondensation of the alkoxysilyl groups, leading to a type II polyvinyl-polysilicate nanocomposite film.
For this, an epoxy resin based on hydrogenated diglycidyl ether bisphenol A was mixed with an epoxy trimethoxysilane precursor (GPTMS, TRIMO) in the presence of photoacid generator based on diaryliodonium salt.
For their synthesis, a preferential route has involved in the successive sol?gel process of acrylate trialkoxysilane precursors followed by radical photopolymerization. The interdependency between the acrylate polymerization and the photoinduced sol-–gel process is kinetically investigated by FTIR.
In this single-step procedure, an epoxy functional reactive resin (EPALLOY 5000) mixed with a variable amount of epoxy trialkoxysilane precursor (TRIMO or GPTMS) was UV-irradiated, causing both the initiation of epoxy ring-opening copolymerization and the catalysis of trialkoxysilyl sol-gel reactions. In this single-step procedure, an epoxy functionalized reactive resin mixed with a variable amount of either of two epoxy trialkoxysilane precursors was UV-irradiated, causing both the initiation of epoxy ring-opening copolymerization and the catalysis of trialkoxysilyl sol-gel reactions.
Through the in situ liberation of protic acids via onium salt photolysis, polymerization of epoxy takes place concomitantly with hydrolysis and condensation of the reactive silanes. 5: These light trains are used to cure fiberglass liners pre-impregnated with UV-curable resin. With its resin in an uncured state, it forms a flexible, conformable tube that can be inserted into a damaged pipe.


The BP plant produces purified terephthalic acid (PTA) and dimethyl 2,6-naphthalene dicarboxylic acid (NDC). When the light hits these photo-initiators, they fracture to form reactive free radicals, which initiate the molecular crosslinking that results in cure. The company makes its liners using Fiberex (Leduc, Alberta, Canada) boron- and fluorine-free E-CR (corrosion-resistant) fiberglass, custom manufactured for StreamLinerUV.
A plastic sheet is pulled into the host pipe to protect the liner from damage as it moves through the host pipe. At that level of chill, heat-cure resins would be more expensive and less efficient, says Richard Herring, project manager for the installer, Construction Unlimited Inc.
Reline patented its own Blue-Tek UV system in 2007, making changes to the equipment and the Light Train.
Active leaking can create cool spots that hinder complete cure by heat-cure methods, but cure by UV light is not affected by cool spots. For installation, after the pipe is thoroughly cleaned and inspected, the preimpregnated liners are winched into the damaged pipe. However, UV liners are limited in thickness and diameter, LightStream’s Montemarano points out.
Insituform’s technology offered a solution of a jointless pipe system and the ability to negotiate bends through its patented method for sewing together the butted ends of its tube, with no overlapping seams that might create distortions and wrinkles in the pipe liner.
Epoxy is almost entirely free of emittable components, and its minimal odor and low shrinkage (3 percent, compared to 7 percent for polyester and vinyl ester resins) recommend it for CIPP applications.
Services uses Perma-Liner’s epoxy system for repair of vitrified clay pipes and concrete pipes that are damaged by root intrusion and heavy soil and to reline cast iron sewer pipe that is corroding on the bottom. It is mated to the host pipe’s interior surface by pushing a torpedo-shaped foam pig (Fig.
This raw material offers the formulator opportunities to develop customized matt overprint varnishes and coatings for flexo and screen applications.
The essential chemistry relies on a spatially controlled photoacid-catalyzed hydrolysis and polycondensation of n-alkyltrimethoxysilane precursors (n-C12H25Si(OCH3)3,).
Real-time Fourier transform IR spectroscopy was instrumental to probe the fast hydrolysis kinetics and assess the change of conformational behavior of the alkyl chains during UV irradiation. Both reaction kinetics were efficiently monitored by real-time Fourier transform infrared spectroscopy, and the influence of different key experimental parameters was investigated (laminated conditions, UV irradiation equipment, and film thickness). Methacrylate and methoxysilyl conversions during irradiation were efficiently monitored by FTIR spectroscopy. Various UV-cured coatings were prepared with different amounts of the hybrid monomer (2 and 5 wt%), and two thicknesses: 15 and 8?m. In contrast, this work presents an original one-step synthesis based on the association of two different photoinitiators (Pls) in the same formulation: the photolysis of a hydroxyphenylketone (radical PI) affords polyacrylate chains while that of a diaryl iodonium salt (cationic PI) generates powerful superacids catalyzing the sol-gel reactions of the alkoxy functions. In addition to the nano-organization study with X-ray diffraction, the mechanical property profiles of the resulting hybrid films are characterized upon combining scratch resistance and nanoindentation analysis.
Effects of UV irradiation on the microstructure of the epoxy-functional polysilsesquioxanes were also studied. The concomitant photoinduced sol-gel process was found to have a significant effect on the two related propagation mechanisms in competition for the oxirane ring-opening: the active chain end and the activated monomer mechanisms, as proved by a systematic examination of the hybrid material microstructure through 29Si and 13C solid state NMR spectroscopy. This straightforward method gives access to a stable, solvent-free and single-component hybrid coating composition, which can be applied at room temperature and cured upon UV exposure. Some sleeves are manufactured inside out and are inverted as they are pushed into the existing pipe via air or water pressure. The other is a fully deteriorated condition, where it is assumed that the existing pipe will be unable to handle any loads sometime over the course of the next 50 years. Petrochemical and other industrial plants, for example, often send highly corrosive media through existing underground metal pipes, resulting in corrosion that must be repaired in a timely manner to prevent groundwater contamination and to avoid work stoppages and delays that interfere with efficient plant operations. However, some CIPP manufacturers have minimized water pollution issues by employing film-encapsulated UV-curable resins and air inflation systems, resulting in no detectable water contamination. UV-curable liners differ from others in that they use a nonwoven glass fiber tube, rather than other nonwovens, because the translucent glass fibers permit light transmission through the liner’s thickness. The liner is preimpregnated with a chemically resistant isopolyester or vinyl ester resin formulated for UV cure, supplied by Momentive (formerly Hexion Specialty Chemicals, Columbus, Ohio). Then the liner is carefully pulled through the old pipe from or to a manhole or other existing opening and inflated with air pressure. The thicker the liner and the farther its surface is from the light source, the less intense, and therefore less effective, the light is at activating the photo initiator.
Faced with the need to repair a sewer pipe that was leaking at the joints under an adjacent parking lot, the center approved the use of a CIPP liner impregnated with styrene-free Atlac Premium 600 vinyl ester, developed specifically for warm-cure CIPP by DSM. The company, a subsidiary of CIPP pioneer Insituform Technologies and now a member of the Aegion Corp. Established in 1998, Perma-Liner focuses specifically on municipal, residential and commercial markets in North America. But epoxy’s solvent-free formulation is enabling CIPP installers to bring no-dig rehabilitation to bear in potable water pipe. But if leading-edge technology is that which sustains and improves the quality of human life, then CIPP certainly qualifies. For screen printing specifically, by using our formulating guide, it can be designed to provide a combination of matt and soft feel properties that can differentiate products in the market. Amphiphilic siloxane species are photogenerated locally and are able to self-assemble spontaneously into a long-range-ordered lamellar mesostructure. The inorganic structure of the resulting silica-based hybrid films was characterized using 29Si solid-state NMR.


The behavior of methacrylate and acrylate trimethoxysilane precursors was compared to highlight the effect of the organic moiety functionality on the reaction kinetics (Fourier transform infrared spectroscopy) and the film microstructure (13C and 29Si solid-state nuclear magnetic resonance).
The effect of the oxo-silica network generation on the epoxy reaction kinetics was also evaluated by RT-FTIR upon varying the epoxysilane structure and its concentration. The effect of the oxo-silica network generation on the epoxy reaction kinetics was also evaluated using real-time Fourier transform infrared spectroscopy upon varying the epoxysilane structure and its concentration. The company’s no-VOC, no-HAP epoxy CIPP provides an eco-sensitive solution for damaged drinking water pipe.
By any name, the underground construction rehabilitation market is a boon to motorists, who suffer fewer delays and take fewer detours. CIPP manufacturers take advantage of polymer resin systems that are resistant to corrosive fluids, even the highly caustic and acidic materials in industrial waste lines.
1, at left) had been corroded by a flow media of process water containing trace amounts of light hydrocarbons from the plant process. Crisler adds that some 83,000 gal (314,190 liters) of water, drawn from the nearby Tennessee River, were circulated to invert, expand and cure the BP liner.
The wetout liner has a six-month shelf life, with no refrigeration required, even in high-temperature environments. The damaged concrete and corrugated metal pipes were under the street and ranged in diameter from 8 inches to 36 inches (203 mm to 914 mm).
As the liner presses against the host pipe, the overlapped layers expand to closely fit the dimensions of the pipe. The CIPP liner was installed by Capital Sewer Services (Hamilton, Ontario, Canada), using nonwoven polyester felt tubes from National Liner LLC (Houston, Texas) that were preimpregnated off site.
These patented systems, designed specifically for CIPP and currently in field trials, crosslink with typical methyl ethyl ketone peroxide (MEKP) catalyst systems that are consistent with standard initiators typically used for CIPP, Hardebeck notes. Notably, epoxy costs more; and, unlike vinyl esters, which can be catalyzed and applied off-site, epoxy must be mixed and applied on-site just before installation. Finally, the reinforcement ability of the resulting hybrid films was also assessed by using a unique range of characterization techniques: DMA, scratch test, and nanoindentation. Interestingly, evidence of local organization in these hybrid films was also given by X-ray analysis. There was a significant slowdown of epoxy conversion rates with increasing sol aging, which may be due to a competition between an active chain end and an activated monomer mechanism for the epoxy cationic polymerization.
Thermal and dynamic mechanical analyses were systematically performed on these hybrids, by studying thoroughly their structure-property interdependence. Thermal and dynamic mechanical analyses were systematically performed on these hybrids, by studying thoroughly their structure-property interdependence. Inversion exposes the as-yet uncured resin to the inside of the pipe, and the external liner then becomes the new internal surface of the pipe.) Others are pulled through damaged pipe.
The UV light source is then drawn through the liner, and curing takes place emission-free between the sealed-off liner ends. That is, the power of the light source is reduced by the inverse square of the distance, Montemarano says. Louis, Mo.), manufactures its own felt tubes using polyester fibers and adds a coat of water-tight polypropylene that bonds with the felt for additional water- and chemical-resistance. Installers aim for complete onsite impregnation of its needle-punched polyvinyl chloride (PVC) felt tubes and polyester scrim.
The liner completely cures in about two hours, after which service connections are restored from within the pipe using a remote-controlled robot. Further, underground construction rehabilitation offers a huge market for the composites industry.
In a last part, their thermomechanical properties were discussed thoroughly using a range of techniques: DSC, scratch-resistance test, nanoindentation. Other mechanical characterizations through tribological and scratch tests suggested that the present photopolymer-silica hybrid material provides a powerful tool to tailor mechanical property profiles.
Factory-impregnated sleeves need only be sealed in light-tight packaging to prevent exposure to sunlight. Capital has continued to use the same AOC nonstyrene system in other Toronto installations. The wetout liners are kept in an ice bath to prevent hardening on site as they wait for installation into the host pipe.
And finally, the finished lined pipe and connections are inspected by a closed-circuit television (CCTV) system. Moreover, because of its low viscosity, the resin has improved flow and more effective pigment wetting. And surely 12.9 percent of $1 trillion is a worthy target to pursue in repair of potable water pipes. There are many possible application areas that can be enhanced with a matt and soft feel experience.
The resin is especially recommended for luxury packaging, direct mail advertising, and high end publication printing.
The light source, camera and heat sensor are connected by umbilical to a programmable logic controller (PLC) and viewed on a monitor by the crew, outside the manhole. Additionally, a standard PC laptop functions as a comprehensive database and communicates with the PLC.



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