iCVD PHEMA Hydrogel Films Crosslink Density Control

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Solution Overview

Problem

Current methods for producing PHEMA thin films lack control over crosslink density, which is crucial for their gel properties and applications such as drug release, and involve wet processes that require solvents and post-treatments, limiting their efficiency and environmental sustainability.

Innovation Solution

Initiated Chemical Vapor Deposition (iCVD) is used to deposit linear and crosslinked PHEMA thin films by feeding a mixture of a monomer, a methacrylate or acrylate crosslinker, and a radical initiator into a vacuum chemical vapor deposition reactor, allowing control of crosslink density through partial pressure adjustments and eliminating the need for solvents.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If wet processes are used to produce PHEMA thin films, then film formation is achieved, but solvents and post-treatments are required which reduces efficiency and environmental sustainability

Engineering Contradiction:
Improvefilm formationVSAvoidprocess time
Core Design Contradiction:
Ease of manufactureVSLoss of time

Solution Approach 1:

The patent replaces wet chemical processes with a vacuum-based chemical vapor deposition process. Instead of using solvents and performing multiple post-treatment steps, the invention uses vacuum CVD to directly deposit crosslinked PHEMA films in a single step, eliminating the need for solvent evaporation and curing operations.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The invention changes the process parameters from liquid-phase wet chemistry to gas-phase vacuum deposition. By controlling the vacuum pressure, monomer flow rates, and substrate temperature, the process achieves direct formation of crosslinked films without requiring separate solvent removal and curing steps.

Inventive Principle:
Principle #35Parameter changes

2Manufacturing precision

If conventional CVD is used, then film deposition is achieved, but crosslink density cannot be controlled which limits gel property optimization

Engineering Contradiction:
Improvefilm depositionVSAvoidcrosslink density control
Core Design Contradiction:
Manufacturing precisionVSMeasurement precision

Solution Approach 1:

The patent implements feedback control by monitoring and adjusting monomer flow rates and vacuum pressure during deposition. This allows real-time control of polymerization kinetics and crosslink density, enabling precise optimization of gel properties for specific applications.

Inventive Principle:
Principle #23Feedback

Solution Approach 2:

The invention controls crosslink density by adjusting the ratio of crosslinking agent to monomer in the gas phase, controlling vacuum pressure levels, and optimizing substrate temperature. These parameter changes enable precise control over the degree of crosslinking and resulting gel properties.

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If PECVD is used to produce PHEMA thin films, then film deposition is achieved, but systematic control of crosslink density has not been demonstrated

Engineering Contradiction:
Improvefilm depositionVSAvoidcrosslink density control
Core Design Contradiction:
Manufacturing precisionVSMeasurement precision

Solution Approach 1:

The patent replaces plasma-based chemistry with vacuum chemical vapor deposition using resistively heated filament wires. This substitution allows for controlled radical generation without the complex plasma chemistry, enabling systematic control of crosslink density through straightforward parameter adjustment.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The invention uses resistive heating to control the temperature of filament wires, which generates radicals for polymerization. By controlling filament temperature and monomer flow rates, the process achieves systematic control of crosslink density that was not possible with PECVD.

Inventive Principle:
Principle #35Parameter changes

4Manufacturing precision

If HFCVD is used, then film deposition is achieved, but multiple steps and high energy input are required which reduces efficiency

Engineering Contradiction:
Improvefilm depositionVSAvoidenergy input
Core Design Contradiction:
Manufacturing precisionVSUse of energy by moving object

Solution Approach 1:

The patent incorporates an initiator into the monomer stream before deposition, so that polymerization and crosslinking begin immediately upon contact with the heated filament. This preliminary preparation eliminates the need for separate initiation steps and reduces total energy input compared to conventional HFCVD.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The invention merges the polymerization, crosslinking, and film deposition steps into a single vacuum CVD process. By combining these operations that would traditionally require separate steps, the process reduces total energy input and improves efficiency.

Inventive Principle:
Principle #5Merging (Combining)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

iCVD enables the production of films with specific crosslink densities, thermal stabilities, and hydrophilic properties, enhancing mechanical properties and enabling controlled drug release while avoiding solvent use and post-treatments, thus improving film quality and environmental sustainability.

Implementation Method 1

resistively-heated filament wires... selective thermal decomposition of species is achieved using resistively-heated filament wires... very low filament temperatures (180-250° C.) are required to generate radicals for initiation

Methodology Applied
Scientific EffectThermal decomposition: Pyrolysis

Implementation Method 2

generate radicals for initiation... These radicals serve as starters of polymer chains

Methodology Applied
Scientific EffectRadical formation: Photodissociation

Implementation Method 3

Chemical vapor deposition (CVD) is a one-step, vacuum process... Initiated CVD (iCVD) can be positioned as a complementary method to PECVD in depositing films with control of crosslink density

Methodology Applied
Scientific EffectChemical vapor deposition: Chemical Vapour Deposition

Implementation Method 4

In another embodiment, iCVD is used to form crosslinked thin films by the addition of a crosslinking agent (e.g., a diacrylate or a dimethyacrylate)... The incorporation of a crosslinking agent into the thin films is shown to increase systematically with its partial pressure

Methodology Applied
Scientific EffectCrosslinking: Chemical Bonding

Implementation Method 5

PHEMA-based hydrogels have been widely researched and used in biomedical applications because of their non-toxicity, non-antigenic properties, and biocompatibility... The unique swelling properties of these films are also disclosed, establishing that certain inventive films function as hydrogels when soaked in water

Methodology Applied
Scientific EffectHydrophilicity: Hydrophile

Data Source

PatentUS7431969B2Chemical vapor deposition of hydrogel films
Publication Date: 2008.10.07 MASSACHUSETTS INST OF TECH
  • US7431969B2 patent drawing
  • US7431969B2 patent drawing
  • US7431969B2 patent drawing

AI summary

In one embodiment of the invention, iCVD is used to form linear thin films using a radical initiator and an alkene. In another embodiment, iCVD is used to form crosslinked thin films by the addition of a crosslinking agent (e.g., a diacrylate or a dimethyacrylate). The incorporation of a crosslinking agent into the thin films is shown to increase systematically with its partial pressure. In one embodiment, when the crosslinker is EDGA and the monomer is HEMA it results in crosslinked P(HEMA-co-EGDA) copolymer. In another embodiment, when the crosslinker is EDGA and the monomer is VP, it results in crosslinked P(VP-co-EGDA). Disclosed are the effects of crosslinker incorporation on the thermal and the wetting properties of the polymers. The unique swelling properties of these films are also described; certain films of the present invention are hydrogels when soaked in water.